谷胱甘肽及衍生物与金属离子相互作用理论研究
摘要
还原性谷胱甘肽（GSH）是细胞内普遍存在的含巯基三肽，在机体防御体系中起重要作用，主要包括清除自由基，防止机体发生脂质氧化，与外源物质或重金属离子结合形成复合物，从而起到解毒的作用。细胞内GSH浓度的降低会引起如糖尿病、人体免疫缺陷病毒感染、囊性纤维变性、急性呼吸窘迫综合症和肾功能衰竭等疾病。对于金属离子，特别是对巯基具有高亲和力的金属离子，通过与GSH结合排出体外，从而也使体内的GSH的含量大大降低。因此，金属与GSH结合是许多金属离子的生物代谢和毒性反应的一个组成部分。而且GSH含有巯基、氨基、羧基、酰胺基等多种配位基团，是研究生物分子与金属离子之间相互作用较理想的模型。因此，研究谷胱甘肽与金属离子的相互作用对探索金属离子在体内生理功能和毒性机理有重要意义。
本文以还原型的GSH为研究对象，采用量子化学方法从理论上对GSH及衍生物与金属离子的相互作用及其光谱性质进行了理论研究。通过对金属离子与GSH相互作用的研究为金属离子生理作用和毒性机理提供理论依据；通过研究Zn~(2+)与谷胱甘肽-邻苯二甲醛（GSH-OPA）的相互作用及其光谱性质，对锌离子增强GSH-OPA荧光的实验现象进行理论解释。主要内容有：
（1）采用密度泛函理论（DFT）计算方法以及AIM和NBO分析方法系统的研究了GSH与碱金属离子(Li~+, Na~+, K~+)、碱土金属离子(Be~(2+), Mg~(2+), Ca~(2+))和Al~(3+)离子相互作用。探讨了金属离子与GSH的结合位点、形成复合物结构和结合能的大小，分析了不同金属离子对GSH构型的影响。研究结果显示：碱土金属离子(Be~(2+), Mg~(2+), Ca~(2+))与GSH的结合能大于碱金属离子(Li~+, Na~+, K~+)与GSH的结合能,碱金属和碱土金属离子都倾向于与GSH分子中的氧原子结合，其次是与N原子，最后是S原子。而且，金属离子与GSH的结合会破坏GSH分子内的氢键，形成新的氢键，甚至使GSH分子内的氢质子发生迁移。与碱金属和碱土金属不同，Al~(3+)在与GSH相互作用过程改变了GSH的骨架结构，部分复合物中巯基的S原子与相邻的酰基氧原子以共价键形式结合，形成了一个五元环。而且，在部分复合物中GSH末端的羧基发生脱羧现象。
（2）采用密度泛函理论（DFT）计算和NBO分析的方法，从几何结构、相互作用能、GSH变形能、金属离子与GSH的给体原子之间的Wiberg键级、键杂化轨道和电荷分析等方面讨论了二价过渡金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+)）和Pb~(2+)与GSH的相互作用。金属离子与GSH的结合能的大小与金属离子的离子势的大小、金属离子的价电子排布、给体原子的类型、配位原子的数目及作用位点都有关。当金属离子与GSH配位方式相同时，同周期过渡金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+),Zn~(2+)）与GSH相互作用大小的变化趋势是：Cu~(2+)≥Ni~(2+)> Co~(2+)> Fe~(2+)> Cr~(2+)> Zn~(2+)> Mn~(2+)。对于同族过渡金属离子（Zn~(2+), Cd~(2+), Hg~(2+)）与GSH相互作用的大小顺序是Zn~(2+)≥Hg~(2+)>Cd~(2+)。NBO分析表明金属离子在与GSH形成复合物的过程中都发生了从配体到金属离子的电荷转移，电荷主要转移到3d和4s轨道，电荷转移量的多少也与其价电子组态有关。Cu~(2+)与GSH之间转移电荷最多，使GSH发生氧化反应的趋势最大，而且部分复合物中Cu~(2+)已经被还原为Cu+。具有d10价电子结构的过渡金属离子（Zn~(2+), Cd~(2+), Hg~(2+)）在与GSH型相互作用过程中转移电荷相对较少，电荷主要转移到更高一层的s轨道。Wiberg键级分析表明金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+), Pb~(2+)）与GSH的配位原子都具有较强的共价性，其中Zn~(2+)、 Cd~(2+)、 Hg~(2+)和Pb~(2+)与S原子的共价性最强。
（3）考察了金属离子的氧化价态、GSH的构型和溶剂化效应对金属离与GSH相互作用的影响，为进一步理解高价态和低价态的同种金属离子在生物体中的生理功能和毒性提供理论依据。在这部分内容中，我们同时模拟了在气相和生物环境内稳定存在的两种构型的GSH（中性和两性离子）与不同价态金属离子（Cr~(2+)、Cr~(3+)、Cr~(6+)、Cu~(2+)、Cu~+、 Hg~(2+)、Hg~+）的相互作用情况。同种金属离子的复合物中，金属离子的电荷越高，半径越小，结合能越大，使GSH的变形程度也越大。金属Cr6+在气相和液相条件与GSH作用都促使了GSH的骨架断裂，发生分子脱羧，这个结果和实验报道Cr6+的毒性大于Cr~(2+)、Cr~(3+)，且能使DNA链发生断裂是一致的。NBO分析表明，在复合物中Cr3+和Cr~(2+)与GSH的O原子之间的共价性大于与S和N原子，Cu~(2+)、Cu+、Hg~(2+)和Hg~+与S、N原子的共价成分大于与O原子。对于铜离子而言，低价态的离子与S、N的共价成分大于高价态的离子。汞离子无论是高价态还是低价态都表现出与S有较强的亲和性，但是Hg~(2+)对S的亲和能力大于Hg~+。与气相计算结果相比，考虑溶剂化效应之后，金属离子与GSH两性离子作用的结合能相对于在气相条件下与中性的GSH相互作用大大降低。而且，对于与GSH的氧原子结合能力大，相互作用中以静电作用为主的金属离子(Cr3+和Cr~(2+))，水溶剂对其结合能的影响最为明显。由于汞离子半径较大，溶剂对其相互作用的影响也很大，一价汞（Hg+）在水液中与GSH两性离子形成的复合物不稳定。
（4）为了更好的理解邻苯二甲醛（OPA）荧光测定GSH的机理以及Zn~(2+)离子对GSH-OPA体系的荧光增强作用，我们从理论上研究了GSH-OPA以及Zn~(2+)与GSH-OPA形成的复合物（GSH-OPA-Zn）的基态和激发态几何结构、吸收和发射光谱性质。采用DFT和HF对基态电子结构优化，在优化好的基态结构基础上采用单电子激发组态相互作用（CIS）对激发态电子结构进行优化，然后通过含时密度泛函方法（TD-DFT）计算GSH-OPA和GSH-OPA-Zn的吸收和发射光谱性质。光谱计算得到的结果和实验报道非常接近，在气相、水和甲醇中，GSH-OPA的最大吸收波长分别是334.6、331.7和331.6nm，实验报道值为340nm左右（在甲醇和水的混合溶液中）。GSH-OPA-Zn在气相有一个明显的LMCT吸收峰(729.2nm)，在水和甲醇中729.2nm处的吸收发生明显的蓝移,分别移至430和460nm。GSH-OPA的发射光谱相对吸收光谱发生了红移，在气相中的最大发射波长为381nm；在水和甲醇中，发射波长位置未发生大的变化，但是振子的强度有所增加。在水和甲醇中，Zn~(2+)的存在并没有使GSH-OPA发射光谱的波长发生位移（主要由π→π*激发引起），但振子强度有所增加。从基态和激发态构型的分析表明Zn~(2+)与GSH-OPA形成复合物后降低了GSH-OPA分子的柔性，增加了分子的刚性，从而增强了GSH-OPA的最大发射波长的振子强度
Reduced glutathione (GSH), a thiol-containing tripeptide, γ-Glu-Cys-Gly, is the most important low molecularweight antioxidant. Glutathione also plays an important role in the complexation and elimination of some toxicmetals from organisms. Due to its important bioactivity and pharmaceutical applications, glutathione has beentargeted by researcher in many fields. Moreover, glutathione molecule possesses all kinds of biological donoratoms: two carboxyls, one thiol, one amino, and two pairs of carbonyl and amide donors within two peptide bonds.Thus, the coordination chemistry of glutathione is of vital importance as it serves as a model system for bindingmetal ions of larger peptide and protein molecules.
In order to better understand the physiological function of the metal ions and the defence mech anism of GSHagainst metal ion toxicity, in this article, a thorough and comparative study of the interactions of metal ions withGSH are conducted using quantum chemistry. Moreover, In order to better understand spectra property of theGSH-OPA and the effect of metal ion on it, the electronic vertical singlet transition energies of the GSH-OPA andthe coordination complex of GSH-OPA with Zn (labeled GSH-OPA-Zn) are also presented in this work. The mainresults are as follows:
(1) Density functional theory methods, AIM and NBO analysis were applied to explore the interaction ofglutathione with metal cations (Li~+, Na~+, K~+, Be~(2+), Mg~(2+), Ca~(2+), Al~(3+)). The different affinity of the studied metalions for different position of GSH, the structure of the complexes, the influence of the metal ions on the structureof GSH have been quantitatively characterized, which are helpful to understand the specific coordination propertyof metal ion in organism. The results show that the intramolecular hydrogen bonds of GSH are broken, newhydrogen bonds are formed, and the hydrogen transfer happened during the coordination process of metal ionswith GSH. Further, the alkali (Li~+, Na~+, K~+) and alkaline earth metal (Be~(2+), Mg~(2+), Ca~(2+)) are inclined tocoordination with oxygen atom of GSH. The trivalent cation Al~(3+)behaves differently with alkali (Li~+, Na~+, K~+)and alkaline metal ions (Be~(2+), Mg~(2+), Ca~(2+)). The change of the GSH structure is significant in presence of Al~(3+)ion.Firstly, the Al~(3+)ion may activate the carboxyl dissociating from GSH. Secondly, it was found that the S atom andO (26) atom of carbonyl was inclined to form covalent bond in Aluminum complexes.
(2) The coordination of GSH with transition metal ions (Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+))and Pb~(2+)are explored using density functional theory method. Through analyze the interaction energies betweenions and GSH, the deformation energies of GSH, the Wiberg Bond Index between acceptor and the donor, hybridbond orbital of complexes and the charge transfer between metal ion and GSH, We discuss the influence of metalions on the structure of GSH and the origin of metal ions selectivity. It is found that the trend of binding energies,deformed energies and the amount of charge transfer are not different in various binding mode. Generally, thebinding energies of Ni~(2+)and Cu~(2+)with GSH are relatively large, Cd~(2+)、Hg~(2+)and Pb~(2+)are relatively small.Moreover, Zn~(2+)、Cd~(2+)、Hg~(2+)and Pb~(2+)are inclined to coordinate with the S atom of GSH, but Cr~(2+)and Mn~(2+)tend tobind with the N and O atom. Furthermore, the Cu~(2+)and Ni~(2+)exhibit strong oxidation to GSH.
(3) In order to understanding the toxicity of metal ion of different valence state, we investigated thecoordination behavior of metal ions (Cr~(2+)、Cr3+、Cr6+、Cu~(2+)、Cu+、Hg~(2+)、Hg+) with GSH using density functionalmethod in gas and water. Two different forms of GSH, corresponding to the prevalent ones in gas-phase (neutralGSH) and in aqueous solution (zwitterionic GSH) are also taken into account. The binding energies of metal ionswith GSH would depend on the size, the charge and the coordination number of the cation, as well as the bindingsite in GSH. Larger the charge of metal ion is, bigger the deformation of GSH is. In presence of Cr6+, themolecular skeleton of GSH is broken and the carboxyl dissociated from GSH no matter in gas phase or in aqueous solution. In the complexes of Cr3+and Cr~(2+), the covalent bonding degree of metal ion with O atom is higher thanthat with S or N atom. However, the Cu~(2+), Cu+, Hg~(2+)and Hg+have higher covalent degree with S and N than thatwith O atom in the complexes. The binding energies of metal ion with zwitterionic GSH in aqueous are muchsmaller than that of the metal ions with the neutral GSH (“basket-like” conformation) in gas phase. Furthermore,the influence of aqueous on the binding energies are various for different metal ion complexes.
(4) In order to better understand spectra property of the GSH-OPA and the effect of metal ion on it, theelectronic vertical singlet transition energies of the GSH-OPA and the coordination complex of GSH-OPA withZn (labeled GSH-OPA-Zn) are presented in this work. The computed absorption maximum of GSH-OPA in gasphase, water and methanol are334.6,331.7and331.6nm, respectively, which compare well with the experimentalvalue (340nm). Coordination of Zn~(2+)to GSH-OPA makes the absorption spectra red shift and gives rise to a newligand-to-metal charge transfer transition at729nm. The red shift of absorption spectra calculated in water andmethanol is smaller than in vacuum. However, the emission band of GSH-OPA at380nm is not observedred-shifted in presence of Zn (Ⅱ) ion. The maximum emission band of GSH-OPA-Zn can be assigned to theGSH-OPA intraligand π*→π transition. The difference of maximum emission band of GSH-OPA andGSH-OPA-Zn are not significant in water and methanol. The computed maximum absorption of GSH-OPA atabout328nm and emission band at380nm compare well with the experimental value. The analysis of thestructure of GSH-OPA and GSH-OPA-Zn indicated that the enhancement of fluorescence of GSH-OPA by Zn~(2+)could be due to the decrease of flexibility of GSH-OPA in present of Zn~(2+).
本文以还原型的GSH为研究对象，采用量子化学方法从理论上对GSH及衍生物与金属离子的相互作用及其光谱性质进行了理论研究。通过对金属离子与GSH相互作用的研究为金属离子生理作用和毒性机理提供理论依据；通过研究Zn~(2+)与谷胱甘肽-邻苯二甲醛（GSH-OPA）的相互作用及其光谱性质，对锌离子增强GSH-OPA荧光的实验现象进行理论解释。主要内容有：
（1）采用密度泛函理论（DFT）计算方法以及AIM和NBO分析方法系统的研究了GSH与碱金属离子(Li~+, Na~+, K~+)、碱土金属离子(Be~(2+), Mg~(2+), Ca~(2+))和Al~(3+)离子相互作用。探讨了金属离子与GSH的结合位点、形成复合物结构和结合能的大小，分析了不同金属离子对GSH构型的影响。研究结果显示：碱土金属离子(Be~(2+), Mg~(2+), Ca~(2+))与GSH的结合能大于碱金属离子(Li~+, Na~+, K~+)与GSH的结合能,碱金属和碱土金属离子都倾向于与GSH分子中的氧原子结合，其次是与N原子，最后是S原子。而且，金属离子与GSH的结合会破坏GSH分子内的氢键，形成新的氢键，甚至使GSH分子内的氢质子发生迁移。与碱金属和碱土金属不同，Al~(3+)在与GSH相互作用过程改变了GSH的骨架结构，部分复合物中巯基的S原子与相邻的酰基氧原子以共价键形式结合，形成了一个五元环。而且，在部分复合物中GSH末端的羧基发生脱羧现象。
（2）采用密度泛函理论（DFT）计算和NBO分析的方法，从几何结构、相互作用能、GSH变形能、金属离子与GSH的给体原子之间的Wiberg键级、键杂化轨道和电荷分析等方面讨论了二价过渡金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+)）和Pb~(2+)与GSH的相互作用。金属离子与GSH的结合能的大小与金属离子的离子势的大小、金属离子的价电子排布、给体原子的类型、配位原子的数目及作用位点都有关。当金属离子与GSH配位方式相同时，同周期过渡金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+),Zn~(2+)）与GSH相互作用大小的变化趋势是：Cu~(2+)≥Ni~(2+)> Co~(2+)> Fe~(2+)> Cr~(2+)> Zn~(2+)> Mn~(2+)。对于同族过渡金属离子（Zn~(2+), Cd~(2+), Hg~(2+)）与GSH相互作用的大小顺序是Zn~(2+)≥Hg~(2+)>Cd~(2+)。NBO分析表明金属离子在与GSH形成复合物的过程中都发生了从配体到金属离子的电荷转移，电荷主要转移到3d和4s轨道，电荷转移量的多少也与其价电子组态有关。Cu~(2+)与GSH之间转移电荷最多，使GSH发生氧化反应的趋势最大，而且部分复合物中Cu~(2+)已经被还原为Cu+。具有d10价电子结构的过渡金属离子（Zn~(2+), Cd~(2+), Hg~(2+)）在与GSH型相互作用过程中转移电荷相对较少，电荷主要转移到更高一层的s轨道。Wiberg键级分析表明金属离子（Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+), Pb~(2+)）与GSH的配位原子都具有较强的共价性，其中Zn~(2+)、 Cd~(2+)、 Hg~(2+)和Pb~(2+)与S原子的共价性最强。
（3）考察了金属离子的氧化价态、GSH的构型和溶剂化效应对金属离与GSH相互作用的影响，为进一步理解高价态和低价态的同种金属离子在生物体中的生理功能和毒性提供理论依据。在这部分内容中，我们同时模拟了在气相和生物环境内稳定存在的两种构型的GSH（中性和两性离子）与不同价态金属离子（Cr~(2+)、Cr~(3+)、Cr~(6+)、Cu~(2+)、Cu~+、 Hg~(2+)、Hg~+）的相互作用情况。同种金属离子的复合物中，金属离子的电荷越高，半径越小，结合能越大，使GSH的变形程度也越大。金属Cr6+在气相和液相条件与GSH作用都促使了GSH的骨架断裂，发生分子脱羧，这个结果和实验报道Cr6+的毒性大于Cr~(2+)、Cr~(3+)，且能使DNA链发生断裂是一致的。NBO分析表明，在复合物中Cr3+和Cr~(2+)与GSH的O原子之间的共价性大于与S和N原子，Cu~(2+)、Cu+、Hg~(2+)和Hg~+与S、N原子的共价成分大于与O原子。对于铜离子而言，低价态的离子与S、N的共价成分大于高价态的离子。汞离子无论是高价态还是低价态都表现出与S有较强的亲和性，但是Hg~(2+)对S的亲和能力大于Hg~+。与气相计算结果相比，考虑溶剂化效应之后，金属离子与GSH两性离子作用的结合能相对于在气相条件下与中性的GSH相互作用大大降低。而且，对于与GSH的氧原子结合能力大，相互作用中以静电作用为主的金属离子(Cr3+和Cr~(2+))，水溶剂对其结合能的影响最为明显。由于汞离子半径较大，溶剂对其相互作用的影响也很大，一价汞（Hg+）在水液中与GSH两性离子形成的复合物不稳定。
（4）为了更好的理解邻苯二甲醛（OPA）荧光测定GSH的机理以及Zn~(2+)离子对GSH-OPA体系的荧光增强作用，我们从理论上研究了GSH-OPA以及Zn~(2+)与GSH-OPA形成的复合物（GSH-OPA-Zn）的基态和激发态几何结构、吸收和发射光谱性质。采用DFT和HF对基态电子结构优化，在优化好的基态结构基础上采用单电子激发组态相互作用（CIS）对激发态电子结构进行优化，然后通过含时密度泛函方法（TD-DFT）计算GSH-OPA和GSH-OPA-Zn的吸收和发射光谱性质。光谱计算得到的结果和实验报道非常接近，在气相、水和甲醇中，GSH-OPA的最大吸收波长分别是334.6、331.7和331.6nm，实验报道值为340nm左右（在甲醇和水的混合溶液中）。GSH-OPA-Zn在气相有一个明显的LMCT吸收峰(729.2nm)，在水和甲醇中729.2nm处的吸收发生明显的蓝移,分别移至430和460nm。GSH-OPA的发射光谱相对吸收光谱发生了红移，在气相中的最大发射波长为381nm；在水和甲醇中，发射波长位置未发生大的变化，但是振子的强度有所增加。在水和甲醇中，Zn~(2+)的存在并没有使GSH-OPA发射光谱的波长发生位移（主要由π→π*激发引起），但振子强度有所增加。从基态和激发态构型的分析表明Zn~(2+)与GSH-OPA形成复合物后降低了GSH-OPA分子的柔性，增加了分子的刚性，从而增强了GSH-OPA的最大发射波长的振子强度
Reduced glutathione (GSH), a thiol-containing tripeptide, γ-Glu-Cys-Gly, is the most important low molecularweight antioxidant. Glutathione also plays an important role in the complexation and elimination of some toxicmetals from organisms. Due to its important bioactivity and pharmaceutical applications, glutathione has beentargeted by researcher in many fields. Moreover, glutathione molecule possesses all kinds of biological donoratoms: two carboxyls, one thiol, one amino, and two pairs of carbonyl and amide donors within two peptide bonds.Thus, the coordination chemistry of glutathione is of vital importance as it serves as a model system for bindingmetal ions of larger peptide and protein molecules.
In order to better understand the physiological function of the metal ions and the defence mech anism of GSHagainst metal ion toxicity, in this article, a thorough and comparative study of the interactions of metal ions withGSH are conducted using quantum chemistry. Moreover, In order to better understand spectra property of theGSH-OPA and the effect of metal ion on it, the electronic vertical singlet transition energies of the GSH-OPA andthe coordination complex of GSH-OPA with Zn (labeled GSH-OPA-Zn) are also presented in this work. The mainresults are as follows:
(1) Density functional theory methods, AIM and NBO analysis were applied to explore the interaction ofglutathione with metal cations (Li~+, Na~+, K~+, Be~(2+), Mg~(2+), Ca~(2+), Al~(3+)). The different affinity of the studied metalions for different position of GSH, the structure of the complexes, the influence of the metal ions on the structureof GSH have been quantitatively characterized, which are helpful to understand the specific coordination propertyof metal ion in organism. The results show that the intramolecular hydrogen bonds of GSH are broken, newhydrogen bonds are formed, and the hydrogen transfer happened during the coordination process of metal ionswith GSH. Further, the alkali (Li~+, Na~+, K~+) and alkaline earth metal (Be~(2+), Mg~(2+), Ca~(2+)) are inclined tocoordination with oxygen atom of GSH. The trivalent cation Al~(3+)behaves differently with alkali (Li~+, Na~+, K~+)and alkaline metal ions (Be~(2+), Mg~(2+), Ca~(2+)). The change of the GSH structure is significant in presence of Al~(3+)ion.Firstly, the Al~(3+)ion may activate the carboxyl dissociating from GSH. Secondly, it was found that the S atom andO (26) atom of carbonyl was inclined to form covalent bond in Aluminum complexes.
(2) The coordination of GSH with transition metal ions (Cr~(2+), Mn~(2+), Fe~(2+), Co~(2+), Ni~(2+), Cu~(2+), Zn~(2+), Cd~(2+), Hg~(2+))and Pb~(2+)are explored using density functional theory method. Through analyze the interaction energies betweenions and GSH, the deformation energies of GSH, the Wiberg Bond Index between acceptor and the donor, hybridbond orbital of complexes and the charge transfer between metal ion and GSH, We discuss the influence of metalions on the structure of GSH and the origin of metal ions selectivity. It is found that the trend of binding energies,deformed energies and the amount of charge transfer are not different in various binding mode. Generally, thebinding energies of Ni~(2+)and Cu~(2+)with GSH are relatively large, Cd~(2+)、Hg~(2+)and Pb~(2+)are relatively small.Moreover, Zn~(2+)、Cd~(2+)、Hg~(2+)and Pb~(2+)are inclined to coordinate with the S atom of GSH, but Cr~(2+)and Mn~(2+)tend tobind with the N and O atom. Furthermore, the Cu~(2+)and Ni~(2+)exhibit strong oxidation to GSH.
(3) In order to understanding the toxicity of metal ion of different valence state, we investigated thecoordination behavior of metal ions (Cr~(2+)、Cr3+、Cr6+、Cu~(2+)、Cu+、Hg~(2+)、Hg+) with GSH using density functionalmethod in gas and water. Two different forms of GSH, corresponding to the prevalent ones in gas-phase (neutralGSH) and in aqueous solution (zwitterionic GSH) are also taken into account. The binding energies of metal ionswith GSH would depend on the size, the charge and the coordination number of the cation, as well as the bindingsite in GSH. Larger the charge of metal ion is, bigger the deformation of GSH is. In presence of Cr6+, themolecular skeleton of GSH is broken and the carboxyl dissociated from GSH no matter in gas phase or in aqueous solution. In the complexes of Cr3+and Cr~(2+), the covalent bonding degree of metal ion with O atom is higher thanthat with S or N atom. However, the Cu~(2+), Cu+, Hg~(2+)and Hg+have higher covalent degree with S and N than thatwith O atom in the complexes. The binding energies of metal ion with zwitterionic GSH in aqueous are muchsmaller than that of the metal ions with the neutral GSH (“basket-like” conformation) in gas phase. Furthermore,the influence of aqueous on the binding energies are various for different metal ion complexes.
(4) In order to better understand spectra property of the GSH-OPA and the effect of metal ion on it, theelectronic vertical singlet transition energies of the GSH-OPA and the coordination complex of GSH-OPA withZn (labeled GSH-OPA-Zn) are presented in this work. The computed absorption maximum of GSH-OPA in gasphase, water and methanol are334.6,331.7and331.6nm, respectively, which compare well with the experimentalvalue (340nm). Coordination of Zn~(2+)to GSH-OPA makes the absorption spectra red shift and gives rise to a newligand-to-metal charge transfer transition at729nm. The red shift of absorption spectra calculated in water andmethanol is smaller than in vacuum. However, the emission band of GSH-OPA at380nm is not observedred-shifted in presence of Zn (Ⅱ) ion. The maximum emission band of GSH-OPA-Zn can be assigned to theGSH-OPA intraligand π*→π transition. The difference of maximum emission band of GSH-OPA andGSH-OPA-Zn are not significant in water and methanol. The computed maximum absorption of GSH-OPA atabout328nm and emission band at380nm compare well with the experimental value. The analysis of thestructure of GSH-OPA and GSH-OPA-Zn indicated that the enhancement of fluorescence of GSH-OPA by Zn~(2+)could be due to the decrease of flexibility of GSH-OPA in present of Zn~(2+).
引文
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