《厦门大学学报（自然科学版）》

半胱氨酸基硫醇配体分子侧链结构对其Ag(Ⅰ)配位聚合物的影响

(Ⅰ)配位聚合物的影响] 吴思娴,陶丹丹,原媛,严小胜,黎朝,江云宝^* (厦门大学化学化工学院,谱学分析与仪器教育部重点实验室,能源材料化学协同创新中心,福建厦门 361005)

关键词：配位聚合物; 硫醇配体; Ag(Ⅰ)-Ag(Ⅰ)相互作用; 氢键; 荧光

Effects of side-chain structures of cysteine-based thiol ligands on their Ag(Ⅰ)coordination polymers

WU Sixian,TAO Dandan,YUAN Yuan,YAN Xiaosheng,LI Zhao,JIANG Yunbao^*

(Key Laboratory of Spectrochemical Analysis & Instrumentation,Ministry of Education,Collaborative Innovation Center of Chemistry for Energy Materials,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

DOI: 10.6043/j.issn.0438-0479.201907025

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设计合成了硫醇类配体N-乙酰-L-半胱氨酰基苯胺(L-1)、N-乙酰-L-半胱氨酰基苯酚酯(L-2)和N-乙酰-L-半胱氨酰基乙酯(L-3),并采用紫外-可见光谱、荧光光谱、圆二色(CD)光谱、动态光散射(DLS)和扫描电子显微镜(SEM)等方法研究了乙醇中L-1～L-3与Ag+配位后的光谱性质和形貌特征.结果表明:L-1和L-3与Ag+形成了配位聚合物,观察到与Ag(Ⅰ)-Ag(Ⅰ)相互作用相关的吸收和荧光光谱信号,但这两个体系的光谱并不相同; 而L-2则与Ag+形成了配位寡聚物,其对应的吸收和荧光光谱信号均较弱且峰波长较短.Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-3配位聚合物体系中还观察到对应吸收的CD信号,意味着手性氨基酸残基的分子手性已传递至超分子聚合物中与Ag(Ⅰ)-Ag(Ⅰ)相互作用相关的生色团上,这归因于配体侧链间的相互作用; 而Ag(Ⅰ)-L-2配位寡聚物体系则无CD信号.据此推测,Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-3配位聚合物中配体侧链间的相互作用可能是氢键作用,且二者的作用模式并不相同.

Three N-acetyl-L-cysteine-based thiol ligands,i.e. its aniline amide(L-1),phenol ester(L-2),and ethanol ester(L-3)were developed and their spectroscopic properties and morphologies in the presence of Ag+ in ethanol were investigated,using a variety of spectral methods such as absorption,fluorescence and circular dichroism(CD)spectroscopy,dynamic light scattering(DLS),and scanning electron microscopy(SEM).It was found that L-1 and L-3 formed coordination polymers with Ag+,respectively,both of which exhibited absorption and fluorescence signals characteristic of the Ag(Ⅰ)-Ag(Ⅰ)interaction,although the signals differed in the two systems.With L-2,however,only coordination oligomers were formed,with much lower absorption and fluorescence signals at shorter wavelengths.CD signals corresponding to the absorption bands were observed with the Ag(Ⅰ)-L-1 and Ag(Ⅰ)-L-3 coordination polymers,suggesting that the molecular chirality of chiral amino acid residues has been transferred to the chromophores related to the Ag(Ⅰ)-Ag(Ⅰ)interactions within the supramolecular polymers,which could be ascribed to the side-chain interactions taking place within each coordination polymer.No CD signal was observed with the Ag(Ⅰ)-L-2 coordination oligomers.Thus the side-chain interactions within the Ag(Ⅰ)-L-1 and Ag(Ⅰ)-L-3 coordination polymers were proposed to be hydrogen bonding,featuring different interaction models in the two cases.

引言
1 实验部分
2 结果与讨论
3 结论

图1 半胱氨酸基手性硫醇配体L-1～L-3的分子结构<br/>Fig.1 Molecular structures of Cys-based chiral thiol ligands L-1 to L-3

图1 半胱氨酸基手性硫醇配体L-1～L-3的分子结构
Fig.1 Molecular structures of Cys-based chiral thiol ligands L-1 to L-3

图2 L-1～L-3的合成路线<br/>Fig.2 Synthetic routes of L-1 to L-3

图2 L-1～L-3的合成路线
Fig.2 Synthetic routes of L-1 to L-3

图3 乙醇中L-1(a)和L-2(b)的吸收光谱随Ag+浓度增加的变化轨迹和吸光度与Ag+浓度的关系曲线(c)<br/>Fig.3 Changes of absorption spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of absorbance versus Ag+ concentration(c)

图3 乙醇中L-1(a)和L-2(b)的吸收光谱随Ag+浓度增加的变化轨迹和吸光度与Ag+浓度的关系曲线(c)
Fig.3 Changes of absorption spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of absorbance versus Ag+ concentration(c)

图4 Ag(Ⅰ)-L-1配位聚合物中配体侧链间氢键作用的模型示意图<br/>Fig.4 Model diagram of hydrogen bond interaction between side-chain of ligand in the Ag(Ⅰ)-L-1 coordination polymer

图4 Ag(Ⅰ)-L-1配位聚合物中配体侧链间氢键作用的模型示意图
Fig.4 Model diagram of hydrogen bond interaction between side-chain of ligand in the Ag(Ⅰ)-L-1 coordination polymer

图5 乙醇中L-1和L-2随Ag+浓度增加时的DLS数据<br/>Fig.5 DLS data of L-1 and L-2 in ethanol with increasing concentration of Ag+

图5 乙醇中L-1和L-2随Ag+浓度增加时的DLS数据
Fig.5 DLS data of L-1 and L-2 in ethanol with increasing concentration of Ag+

图6 乙醇中L-1(a)和L-2(b)的荧光光谱随Ag+浓度增加的变化轨迹和荧光强度与Ag+浓度的关系曲线(c)<br/>Fig.6 Changes of fluorescence spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of fluorescence intensity versus Ag+ concentration(c)

图6 乙醇中L-1(a)和L-2(b)的荧光光谱随Ag+浓度增加的变化轨迹和荧光强度与Ag+浓度的关系曲线(c)
Fig.6 Changes of fluorescence spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of fluorescence intensity versus Ag+ concentration(c)

图7 乙醇中L-1(a)和L-2(b)的CD光谱随Ag+浓度增加的变化轨迹和CD信号与Ag+浓度的关系曲线(c)<br/>Fig.7 Changes of CD spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of CD signals versus Ag+ concentration(c)

图7 乙醇中L-1(a)和L-2(b)的CD光谱随Ag+浓度增加的变化轨迹和CD信号与Ag+浓度的关系曲线(c)
Fig.7 Changes of CD spectra of L-1(a)and L-2(b)in ethanol with increasing concentration of Ag+ and plots of CD signals versus Ag+ concentration(c)

图8 乙醇(a)和甲醇(b)中L-1的荧光光谱随Ag+浓度增加的变化轨迹和荧光强度与Ag+浓度的关系曲线(c)<br/>Fig.8 Changes of fluorescence spectra of L-1 in ethanol(a)and methanol(b)with increasing concentration of Ag+ and plots of fluorescence intensity versus Ag+ concentration(c)

图8 乙醇(a)和甲醇(b)中L-1的荧光光谱随Ag+浓度增加的变化轨迹和荧光强度与Ag+浓度的关系曲线(c)
Fig.8 Changes of fluorescence spectra of L-1 in ethanol(a)and methanol(b)with increasing concentration of Ag+ and plots of fluorescence intensity versus Ag+ concentration(c)

图9 CH3OH和CD3OD中Ag(Ⅰ)-L-1(a, 520 nm)和Ag(Ⅰ)-L-2(b, 480 nm)的荧光强度随时间的变化轨迹<br/>Fig.9 Changes of fluorescence intensity of Ag(Ⅰ)-L-1 (a,520 nm)and Ag(Ⅰ)-L-2(b,480 nm) in CH3OH and CD3OD with time

图9 CH3OH和CD3OD中Ag(Ⅰ)-L-1(a, 520 nm)和Ag(Ⅰ)-L-2(b, 480 nm)的荧光强度随时间的变化轨迹
Fig.9 Changes of fluorescence intensity of Ag(Ⅰ)-L-1 (a,520 nm)and Ag(Ⅰ)-L-2(b,480 nm) in CH3OH and CD3OD with time

图10 Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-2的SEM图<br/>Fig.10 SEM images of Ag(Ⅰ)-L-1 and Ag(Ⅰ)-L-2

图10 Ag(Ⅰ)-L-1和Ag(Ⅰ)-L-2的SEM图
Fig.10 SEM images of Ag(Ⅰ)-L-1 and Ag(Ⅰ)-L-2

图11 乙醇中L-3的吸收(a)、CD(b)和荧光(c)光谱随Ag+浓度增加的变化轨迹<br/>Fig.11 Changes of absorption(a),CD(b)and fluorescence(c)spectra of L-3 in ethanol with increasing concentration of Ag+

图11 乙醇中L-3的吸收(a)、CD(b)和荧光(c)光谱随Ag+浓度增加的变化轨迹
Fig.11 Changes of absorption(a),CD(b)and fluorescence(c)spectra of L-3 in ethanol with increasing concentration of Ag+

图12 乙醇溶液中不同配体与Ag+作用形成的物种的DLS数据<br/>Fig.12 DLS data of species formed by the interaction of different ligands and Ag+ in ethanol solution

图12 乙醇溶液中不同配体与Ag+作用形成的物种的DLS数据
Fig.12 DLS data of species formed by the interaction of different ligands and Ag+ in ethanol solution

图13 Ag(Ⅰ)-L-3配位聚合物中配体侧链间氢键作用的模型示意图<br/>Fig.13 A possible inter-ligand hydrogen bonding model in the Ag(Ⅰ)-L-3 coordination polymer

图13 Ag(Ⅰ)-L-3配位聚合物中配体侧链间氢键作用的模型示意图
Fig.13 A possible inter-ligand hydrogen bonding model in the Ag(Ⅰ)-L-3 coordination polymer

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《厦门大学学报（自然科学版）》于1931年创刊，是由教育部主管，厦门大学主办，国内外公开发行的综合性学术期刊（双月刊），是我国自然科学核心期刊。本刊以印刷版、网络版的方式同时出版。主要刊载自然科学各学科的最新研究成果，包括自然科学基础理论研究、应用基础研究、高新技术方面的学术论文。所刊载的论文分三大类型：（1）“快讯”：报道某前沿领域具有突破性的最新研究成果。（2）“研究论文”：刊载理工科基础理论研究与实验研究学术论文。（3）“研究简报”：刊载内容新颖、实用（或阶段性）的成果。更多>>

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引言

1 实验部分

2 结果与讨论

3 结 论

学报简介

3 结论