XAS Investigation of Silver(I) Coordination in Copper(I) Biological Binding Sites

化学 金属硫蛋白 X射线吸收光谱法 结晶学 配位复合体 协调数 结合位点 螯合作用 粘结长度 立体化学 伴侣(临床) 金属 无机化学 离子 吸收光谱法 晶体结构 生物化学 有机化学 物理 量子力学 医学 病理
作者
Giulia Veronesi,Thomas Gallon,Aurélien Deniaud,Bastien Boff,Christelle Gateau,Colette Lebrun,Claude Vidaud,Françoise Rollin-Genetet,Marie Carrière,Isabelle Kieffer,Elisabeth Mintz,Pascale Delangle,Isabelle Michaud‐Soret
出处
期刊:Inorganic Chemistry [American Chemical Society]
卷期号:54 (24): 11688-11696 被引量:31
标识
DOI:10.1021/acs.inorgchem.5b01658
摘要

Silver(I) is an unphysiological ion that, as the physiological copper(I) ion, shows high binding affinity for thiolate ligands; its toxicity has been proposed to be due to its capability to replace Cu(I) in the thiolate binding sites of proteins involved in copper homeostasis. Nevertheless, the nature of the Ag(I)–thiolate complexes formed within cells is poorly understood, and the details of Ag(I) coordination in such complexes in physiologically relevant conditions are mostly unknown. By making use of X-ray absorption spectroscopy (XAS), we characterized the Ag(I) binding sites in proteins related to copper homeostasis, such as the chaperone Atox1 and metallothioneins (MTs), as well as in bioinspired thiolate Cu(I) chelators mimicking these proteins, in solution and at physiological pH. Different Ag(I) coordination environments were revealed: the Ag–S bond length was found to correlate to the Ag(I) coordination number, with characteristic values of 2.40 and 2.49 Å in AgS2 and AgS3 sites, respectively, comparable to the values reported for crystalline Ag(I)–thiolate compounds. The bioinspired Cu(I) chelator L1 is proven to promote the unusual trigonal AgS3 coordination and, therefore, can serve as a reference compound for this environment. In the Cu(I)-chaperone Atox1, Ag(I) binds in digonal coordination to the two Cys residues of the Cu(I) binding loop, with the AgS2 characteristic bond length of 2.40 ± 0.01 Å. In the multinuclear Ag(I) clusters of rabbit and yeast metallothionein, the average Ag–S bond lengths are 2.48 ± 0.01 Å and 2.47 ± 0.01 Å, respectively, both indicative of the predominance of trigonal AgS3 sites. This work lends insight into the coordination chemistry of silver in its most probable intracellular targets and might help in elucidating the mechanistic aspects of Ag(I) toxicity.

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
大幅提高文件上传限制,最高150M (2024-4-1)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
AHUAMM完成签到,获得积分10
1秒前
好的发布了新的文献求助200
1秒前
Jasper应助顶顶顶采纳,获得10
1秒前
2秒前
坦率抽屉完成签到 ,获得积分10
3秒前
香蕉觅云应助moxi摩西采纳,获得10
6秒前
CodeCraft应助donny采纳,获得10
6秒前
777完成签到,获得积分20
7秒前
9秒前
coolulu发布了新的文献求助10
9秒前
Renhong应助矮小的路人采纳,获得10
10秒前
孤独念柏完成签到,获得积分10
10秒前
温柔孤兰发布了新的文献求助10
12秒前
13秒前
13秒前
CXSCXD发布了新的文献求助10
13秒前
传奇3应助武雨寒采纳,获得10
14秒前
SciGPT应助吴世宇采纳,获得30
16秒前
阳光代丝完成签到 ,获得积分10
17秒前
恐龙植树发布了新的文献求助10
18秒前
bkagyin应助灰灰采纳,获得10
18秒前
传奇3应助自然的致远采纳,获得10
18秒前
能干砖家完成签到,获得积分10
19秒前
小羊发布了新的文献求助10
20秒前
Res_M发布了新的文献求助30
21秒前
23秒前
23秒前
通天塔完成签到,获得积分10
25秒前
魔幻傲晴完成签到 ,获得积分10
25秒前
恐龙植树完成签到,获得积分10
25秒前
温柔孤兰发布了新的文献求助10
27秒前
矮小的路人完成签到,获得积分10
28秒前
28秒前
30秒前
33秒前
digger2023发布了新的文献求助10
35秒前
小二郎应助zwl采纳,获得10
35秒前
vhdadw完成签到,获得积分10
36秒前
36秒前
NexusExplorer应助小张采纳,获得10
37秒前
高分求助中
The late Devonian Standard Conodont Zonation 2000
Nickel superalloy market size, share, growth, trends, and forecast 2023-2030 2000
The Lali Section: An Excellent Reference Section for Upper - Devonian in South China 1500
Very-high-order BVD Schemes Using β-variable THINC Method 870
Mantiden: Faszinierende Lauerjäger Faszinierende Lauerjäger 800
PraxisRatgeber: Mantiden: Faszinierende Lauerjäger 800
Fundamentals of Dispersed Multiphase Flows 500
热门求助领域 (近24小时)
化学 医学 生物 材料科学 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 基因 遗传学 催化作用 物理化学 免疫学 量子力学 细胞生物学
热门帖子
关注 科研通微信公众号,转发送积分 3254201
求助须知:如何正确求助?哪些是违规求助? 2896520
关于积分的说明 8292993
捐赠科研通 2565415
什么是DOI,文献DOI怎么找? 1393024
科研通“疑难数据库(出版商)”最低求助积分说明 652418
邀请新用户注册赠送积分活动 629880