具有接力识别功能的荧光探针研究进展

接力识别是一种操作简单并逐渐被广泛使用的离子识别方法。本文介绍了接力识别的意义和类型,详细地介绍了近年来包括金属离子和阴离子、阴离子和金属离子、金属离子和金属离子以及阴离子和阴离子的接力型荧光识别研究进展,以期为设计合成新颖的具有接力识别功能的荧光探针提供参考。     

Recognition of mandelate stereoisomers by chiral porphyrin hosts: prediction of stereopreference in guest binding a priori using a simple binding model?

Rigid porphyrin hosts that mimic the spatial arrangement of mandelate recognition motifs lead to stereoselective receptors and illustrate how subtle structural differences in host design have significant impact on guest recognition. The porphyrin hosts are obtained with minimal synthetic effort from readily available chiral amine precursors and are modular in design. The chiral recognition properties of the porphyrin-based hosts with chiral carboxylate-containing guests and chiral amines are described. UV/vis and ¹H NMR spectroscopic results indicate some of these porphyrin hosts undergo an induced fit conformational change upon guest binding.     

一种基于偶氮水杨醛酰腙的CN-探针

设计合成了一种基于偶氮苯基团的简单而高效的比色探针L1,并利用紫外-可见吸收光谱考察其对阴离子（F^-, Cl^-, Br^-, I^-, AcO^-, H₂PO₄^-, HSO₄^-, ClO₄^-和CN^-）的识别性能。结果表明：探针L1在DMSO/H₂O（5：5, V/V）的含水体系中,可以实现对CN^-单一选择性识别;且加入CN^-时,溶液颜色立刻由无色变为红色,而加入其它阴离子则无变化,说明该探针能够实现对CN^-的裸眼识别。另外,该探针对CN^-的检测灵敏度较高,最低检测限达到了1.3 μmol·L^-1。此外,我们制作了负载有探针分子L1的试纸条,能够更加方便快捷的检测CN^-。     

一种基于偶氮水杨醛酰腙的CN-探针

设计合成了一种基于偶氮苯基团的简单而高效的比色探针L1,并利用紫外-可见吸收光谱考察其对阴离子(F-,Cl-,Br-,I-,AcO-,H2PO4-,HSO4-,ClO4-和CN-)的识别性能。结果表明:探针L1在DMSO/H2O(5∶5,V/V)的含水体系中,可以实现对CN-单一选择性识别;且加入CN-时,溶液颜色立刻由无色变为红色,而加入其它阴离子则无变化,说明该探针能够实现对CN-的裸眼识别。另外,该探针对CN-的检测灵敏度较高,最低检测限达到了1.3μmol·L-1。此外,我们制作了负载有探针分子L1的试纸条,能够更加方便快捷的检测CN-。     

Pattern-based peptide recognition

Nature's use of sensor arrays in the mammalian olfactory and gustatory systems has encouraged supramolecular chemists to take a new approach to molecular recognition. Pattern-based recognition involves the use of sensor arrays to create fingerprints for analytes. The use of sensing arrays has paved the way for systems capable of identifying biological analytes that would have been difficult targets using the traditional "lock-and-key" approach to sensor design.     

Recognizing chromatographic peaks with pattern recognition methods III. Application of the algorithm for peak recognition in trace analysis

Summary The application of a newly developed peak recognition algorithm is shown. This algorith is based on the KNN method, one of the pattern recognition methods. It is shown that peaks with a S/N-ratio down to one can be safely recognized. This is also possible if the baseline has not only detector noise, but has other disturbances, e.g., noise signals which are generated by a reaction detector. The recognition ability of the algorithm is demonstrated by a standard chromatogram with three different concentrations and with two different sampling rates. The improvement against the classical algorithm is demonstrated. Some properties of the algorithm are discussed.     

N-芳基香豆素甲基酮缩氨基硫脲对Cu2+的选择性比色识别

设计合成了2种新型N-芳基香豆素甲基酮缩氨基硫脲受体分子S1和S2, 利用紫外-可见(UV-Vis)吸收光谱考察了其对Fe3+, Hg2+, Ag+, Ca2+, Cu2+, Zn2+, Pb2+, Cd2+, Ni2+, Cr3+和Mg2+等阳离子的识别作用. 结果表明, 当加入Cu2+时, 溶液颜色立刻由无色变为黄色, 而加入其它阳离子则无变化, 从而实现了对Cu2+的裸眼检测, 具有专一选择性比色识别效果. 通过计算可知, 受体分子S2对Cu2+的络合常数大于S1, 且主客体间形成1: 1的配合物. 受体分子S2对Cu2+的检出限为2.0×10-7 mol/L, 稳定常数Ks=1.02×105 L/mol. 另外, 在EDTA存在时, 配合物可以释放出Cu2+, 与EDTA结合, 表现出对Cu2+的"off-on"模式.     

An efficient sensor for relay recognition of Zn and Cu through fluorescence ‘off–on–off’ functionality

A new bis(8-carboxamidoquinoline) dangled binaphthol derivatized fluorescent sensor (L) was designed and synthesized. L behaves ratiometric response to Zn²⁺ with high selectivity accompanied by remarkable emission enhancement and red shift. The resultant L–Zn²⁺ complex can act as a Cu²⁺ sensing probe with fluorescence quenching behavior through direct Zn²⁺ ion replacement. Furthermore, the binding modes of Zn²⁺ and Cu²⁺ with L are elucidated by X-ray crystallographic analysis, respectively.     

杯芳烃衍生物对阴离子的识别作用

综述了杯芳烃衍生物对阴离子识别作用的研究进展。详细介绍了杯芳烃衍生物的化学结构修饰和分子结构以及其通过氢键和静电等作用对卤素、有机酸根、金属酸根等阴离子的识别作用,并对其应用前景进行了展望。     

三维人脸识别算法研究

近年来,基于三维图像的人脸识别技术已经取得了很大进展,在约束环境下也能获得很好的识别性能,但仍受限于姿态、表情等因素,需要从算法上改进才能解决其影响。本文分别从基于空域直接匹配、基于局部特征匹配和基于整体特征匹配3个角度出发,对人脸匹配算法以及融合算法进行了研究,列出了部分改进算法的实验结果,并分析了算法有效性的原因,总结了目前面临的三维人脸识别算法难以突破的一些困难及未来的研究趋势。     

4-氨基-7-硝基苯并-2-氧杂-1,3-二唑类衍生物的合成及其对汞离子的识别研究

以4-氯-7-硝基苯并-2-氧杂-1,3-二唑、乙二胺和溴乙酸乙酯等为原料,合成4-氨基-7-硝基苯并-2-氧杂-1,3-二唑类衍生物(NBD-OEt),通过IR、NMR和MS对其进行结构表征。研究NBD-OEt的吸收光谱和荧光光谱性质,探讨其在H2O/EtOH(60/40, V/V) pH 7.40的HEPES缓冲体系中对Hg₂ 的响应,以及NBD-OEt与Hg₂ 的结合模式。结果表明, 随Hg₂ 的不断加入可诱使NBD-OEt在476nm的吸收峰红移至514nm,并有两个等吸收点(347nm、482nm);其荧光发射峰由536nm红移至559nm,且在525nm出现等发射点;通过Job plot法测定NBD-OEt与Hg₂ 以1:1的计量比结合。     

基于酰腙和酚羟基的阴离子受体的合成及其在含水介质中的阴离子比色识别性能

设计合成了一系列基于羟基和氨基的酰腙类受体分子.利用紫外-可见吸收光谱及1HNMR考察了其与F-,Cl-,Br-,I-,CH3COO-,H2PO4?,HSO4?,ClO?4等阴离子的作用.结果表明,该类受体分子在DMSO溶液中能较好地比色识别F-,CH3COO-,H2PO4?,其中受体2在含水介质中[V(DMSO)∶V(H2O)=7∶3]能选择性比色识别CH3COO-.1HNMR滴定实验研究了受体分子与阴离子之间的作用,结果表明受体分子与阴离子之间以氢键作用方式相结合.     

汞离子的高灵敏度裸眼识别和荧光传感探针

设计合成了一种以耐尔蓝为母体的Hg2+光学探针分子1-苯甲酰-3-{2-[9-(乙氨基)-10-甲基-9H-苯并[α]苯酚-5-胺基]乙基}硫脲盐酸盐(NBET). 在pH=7.4的Tris-HCl缓冲液中, 探针分子最大吸收波长为640 nm, 此时溶液为淡蓝色; 加入汞离子可以诱导探针分子在640 nm处的吸收降低, 并在556 nm处产生新的吸收峰, 溶液变为浅紫色, 而其它金属离子的加入未引起显著变化, 基于此可对水溶液中的痕量Hg2+进行裸眼识别. 荧光光谱显示, 汞离子可以特异性地猝灭探针分子在660 nm处的荧光发射. 该探针分子的灵敏度、选择性及荧光量子产率高, 激发/发射波长长, 可以实现水溶液中0.005 μmol/L Hg2+的荧光检测.     

Supramolecular Sensor for Astringent Procyanidin C1: Fluorescent Artificial Tongue for Wine Components

An artificial tongue that detects astringent components for a comprehensive evaluation of taste has not been established to date. Herein, we first propose fluorescent polythiophene (PT) derivatives ( S1 – S3 ) modified with 3-pyridinium boronic acid as supramolecular chemosensors for wine components including astringent procyanidin C1. After numerous attempts for the synthetic conditions, more than 95 mol % of the PT unit was modified with the pyridinium boronic acid moiety. To evaluate the PT derivatives as chemosensors of the artificial tongue, qualitative and quantitative analyses were performed with four types of wine components (i.e., sweet, sour, bitter, and astringent tastes) in combination with pattern recognition models. Notably, procyanidin C1 in the actual wine sample was successfully detected in a quantitative manner. In other words, we have established an authentic artificial tongue using PT based supramolecular chemosensors.