• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

用于表征顺磁性/自旋交叉配位络合物和金属有机笼的顺磁性核磁共振光谱工具箱

A Paramagnetic NMR Spectroscopy Toolbox for the Characterisation of Paramagnetic/Spin-Crossover Coordination Complexes and Metal-Organic Cages.

作者信息

Lehr Marc, Paschelke Tobias, Trumpf Eicke, Vogt Anna-Marlene, Näther Christian, Sönnichsen Frank D, McConnell Anna J

机构信息

Otto Diels Institute of Organic Chemistry, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, Kiel, 24098, Germany.

Institute of Inorganic Chemistry, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel, 24118, Germany.

出版信息

Angew Chem Int Ed Engl. 2020 Oct 19;59(43):19344-19351. doi: 10.1002/anie.202008439. Epub 2020 Aug 26.

DOI:10.1002/anie.202008439
PMID:33448544
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7590057/
Abstract

The large paramagnetic shifts and short relaxation times resulting from the presence of a paramagnetic centre complicate NMR data acquisition and interpretation in solution. As a result, NMR analysis of paramagnetic complexes is limited in comparison to diamagnetic compounds and often relies on theoretical models. We report a toolbox of 1D (H, proton-coupled C, selective H-decoupling C, steady-state NOE) and 2D (COSY, NOESY, HMQC) paramagnetic NMR methods that enables unprecedented structural characterisation and in some cases, provides more structural information than would be observable for a diamagnetic analogue. We demonstrate the toolbox's broad versatility for fields from coordination chemistry and spin-crossover complexes to supramolecular chemistry through the characterisation of Co and high-spin Fe mononuclear complexes as well as a CoL cage.

摘要

顺磁中心的存在导致的大的顺磁位移和短的弛豫时间使溶液中的核磁共振（NMR）数据采集和解释变得复杂。因此，与抗磁性化合物相比，顺磁配合物的NMR分析受到限制，并且通常依赖于理论模型。我们报告了一个包含一维（氢、质子耦合碳、选择性氢去耦碳、稳态核Overhauser效应（NOE））和二维（化学位移相关谱（COSY）、核Overhauser效应谱（NOESY）、异核多量子相干谱（HMQC））顺磁NMR方法的工具箱，该工具箱能够实现前所未有的结构表征，并且在某些情况下，提供的结构信息比抗磁性类似物可观测到的更多。通过对钴和高自旋铁单核配合物以及一个钴配体笼的表征，我们展示了该工具箱在从配位化学、自旋交叉配合物到超分子化学等领域的广泛通用性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/aa9023d9d31e/ANIE-59-19344-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/9aa5cedd3ddb/ANIE-59-19344-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/362ec1643ea3/ANIE-59-19344-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/bcda6430107c/ANIE-59-19344-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/2faae250f3b1/ANIE-59-19344-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/aa9023d9d31e/ANIE-59-19344-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/9aa5cedd3ddb/ANIE-59-19344-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/362ec1643ea3/ANIE-59-19344-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/bcda6430107c/ANIE-59-19344-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/2faae250f3b1/ANIE-59-19344-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/aff1/7590057/aa9023d9d31e/ANIE-59-19344-g005.jpg

相似文献

1
A Paramagnetic NMR Spectroscopy Toolbox for the Characterisation of Paramagnetic/Spin-Crossover Coordination Complexes and Metal-Organic Cages.用于表征顺磁性/自旋交叉配位络合物和金属有机笼的顺磁性核磁共振光谱工具箱
Angew Chem Int Ed Engl. 2020 Oct 19;59(43):19344-19351. doi: 10.1002/anie.202008439. Epub 2020 Aug 26.
2
Predicting paramagnetic 1H NMR chemical shifts and state-energy separations in spin-crossover host-guest systems.预测自旋交叉主客体体系中的顺磁1H NMR化学位移和态-能分离。
Phys Chem Chem Phys. 2014 Jun 14;16(22):10620-8. doi: 10.1039/c4cp01478b.
3
31P NMR probes of chemical dynamics: paramagnetic relaxation enhancement of the (1)H and (31)P NMR resonances of methyl phosphite and methylethyl phosphate anions by selected metal complexes.化学动力学的31P NMR探针：特定金属配合物对亚磷酸甲酯和磷酸甲乙酯阴离子的(1)H和(31)P NMR共振的顺磁弛豫增强作用
Inorg Chem. 2001 Dec 17;40(26):6547-54. doi: 10.1021/ic010728w.
4
Solution structural characteristics of cyanometmyoglobin: resonance assignment of heme cavity residues by two-dimensional NMR.氰化高铁肌红蛋白的溶液结构特征：通过二维核磁共振对血红素腔残基进行共振归属
Biochemistry. 1990 Feb 13;29(6):1545-56. doi: 10.1021/bi00458a028.
5
2D NMR of paramagnetic metalloenzymes: cyanide-inhibited horseradish peroxidase.顺磁性金属酶的二维核磁共振：氰化物抑制的辣根过氧化物酶
J Biomol NMR. 1991 Jul;1(2):175-90. doi: 10.1007/BF01877229.
6
Paramagnetic NMR investigations of high-spin nickel(II) complexes. Controlled synthesis, structural, electronic, and magnetic properties of dinuclear vs. mononuclear species.高自旋镍（II）配合物的顺磁核磁共振研究。双核与单核物种的可控合成、结构、电子和磁性性质。
J Am Chem Soc. 2001 Aug 22;123(33):8053-66. doi: 10.1021/ja010342k.
7
Solution structure of the paramagnetic complex of the N-terminal domain of calmodulin with two Ce3+ ions by 1H NMR.通过1H NMR测定钙调蛋白N端结构域与两个Ce3+离子的顺磁复合物的溶液结构
Biochemistry. 1997 Sep 30;36(39):11605-18. doi: 10.1021/bi971022+.
8
Complete sequence-specific 1H NMR resonance assignment of hyperfine-shifted residues in the active site of a paramagnetic protein: application to Aplysia cyano-metmyoglobin.顺磁蛋白活性位点中超精细位移残基的完整序列特异性 1H NMR 共振归属：应用于海兔氰化高铁肌红蛋白
J Biomol NMR. 1992 Nov;2(6):597-618. doi: 10.1007/BF02192849.
9
A new approach in 1D and 2D 13C high-resolution solid-state NMR spectroscopy of paramagnetic organometallic complexes by very fast magic-angle spinning.一种通过极快速魔角旋转对顺磁有机金属配合物进行一维和二维¹³C高分辨率固态核磁共振光谱分析的新方法。
J Am Chem Soc. 2003 Mar 26;125(12):3438-9. doi: 10.1021/ja0291742.
10
Strategy for the study of paramagnetic proteins with slow electronic relaxation rates by nmr spectroscopy: application to oxidized human [2Fe-2S] ferredoxin.通过核磁共振光谱研究具有缓慢电子弛豫速率的顺磁性蛋白质的策略：应用于氧化型人[2Fe-2S]铁氧还蛋白
J Am Chem Soc. 2004 May 5;126(17):5413-26. doi: 10.1021/ja037077i.

引用本文的文献

1
A Comprehensive Study of the Cobalt(II) Chelation Mechanism by an Iminodiacetate-Decorated Disaccharide Ligand.亚氨基二乙酸修饰的二糖配体对钴（II）螯合机制的综合研究
Molecules. 2025 Aug 4;30(15):3263. doi: 10.3390/molecules30153263.
2
Modulation of Lanthanide Luminescence with the Mechanical Bond: Antenna-Emitter Confinement in a Compact [2]Rotaxane.利用机械键调控镧系元素发光：紧凑型[2]轮烷中的天线-发光体限制作用
Angew Chem Int Ed Engl. 2025 Aug 4;64(32):e202505666. doi: 10.1002/anie.202505666. Epub 2025 Jun 16.
3
Selective Sequestration of Palladium(II) Cations Using a Supramolecular Polymer Approach.

本文引用的文献

1
Heterobifunctional Rotaxanes for Asymmetric Catalysis.用于不对称催化的异双功能轮烷
Angew Chem Int Ed Engl. 2020 Mar 23;59(13):5102-5107. doi: 10.1002/anie.201913781. Epub 2020 Jan 16.
2
Dynamic Complex-to-Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions.异双金属体系的动态复-复转变影响铁（II）离子的笼状结构或自旋态。
Angew Chem Int Ed Engl. 2020 Feb 17;59(8):3195-3200. doi: 10.1002/anie.201914629. Epub 2020 Jan 9.
3
Adding diffusion ordered NMR spectroscopy (DOSY) to the arsenal for characterizing paramagnetic complexes.
使用超分子聚合物方法选择性螯合钯（II）阳离子。
Chemistry. 2025 Jun 3;31(31):e202500392. doi: 10.1002/chem.202500392. Epub 2025 May 13.
4
Probing substrate binding inside a paramagnetic cavity: a NMR spectroscopy toolbox for combined experimental and theoretical investigation.探索顺磁腔内的底物结合：用于实验与理论联合研究的核磁共振光谱工具箱
Chem Sci. 2024 Sep 24;15(42):17407-17. doi: 10.1039/d4sc05432f.
5
Apoptosis Induction in HepG2 and HCT116 Cells by a Novel Quercetin-Zinc (II) Complex: Enhanced Absorption of Quercetin and Zinc (II).新型槲皮素-锌（II）配合物诱导 HepG2 和 HCT116 细胞凋亡：增强了槲皮素和锌（II）的吸收。
Int J Mol Sci. 2023 Dec 14;24(24):17457. doi: 10.3390/ijms242417457.
6
Confinement inside MOFs Enables Guest-Modulated Spin Crossover of Otherwise Low-Spin Coordination Cages.金属有机框架内的限域作用实现了客体调制的自旋交叉，否则这些低自旋配位笼无法实现自旋交叉。
JACS Au. 2023 Jul 28;3(8):2183-2191. doi: 10.1021/jacsau.3c00243. eCollection 2023 Aug 28.
7
Studying Peptide-Metal Ion Complex Structures by Solution-State NMR.通过溶液态 NMR 研究肽-金属离子配合物结构。
Int J Mol Sci. 2022 Dec 15;23(24):15957. doi: 10.3390/ijms232415957.
8
Light-Controlled Destruction and Assembly: Switching between Two Differently Composed Cage-Type Complexes.光控破坏与组装：在两种不同组成的笼型配合物之间进行切换。
Angew Chem Int Ed Engl. 2023 Jan 2;62(1):e202212571. doi: 10.1002/anie.202212571. Epub 2022 Nov 29.
9
Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes.顺磁性固态核磁共振归属以及铜（II）和钴（II）-吡啶甲醛配合物中醛基向二氢酯和半缩醛部分的新型化学转化
RSC Adv. 2021 Jun 9;11(33):20216-20231. doi: 10.1039/d1ra02512k. eCollection 2021 Jun 3.
10
A Family of Heterobimetallic Cubes Shows Spin-Crossover Behaviour Near Room Temperature.一类异双金属立方体在室温附近呈现自旋交叉行为。
Angew Chem Int Ed Engl. 2021 Oct 4;60(41):22562-22569. doi: 10.1002/anie.202108792. Epub 2021 Sep 6.
为了更好地描述顺磁配合物，将扩散排序核磁共振波谱（DOSY）纳入武器库。
Chem Commun (Camb). 2019 Nov 28;55(96):14426-14429. doi: 10.1039/c9cc08229h.
4
A Redox-Switchable Molecular Zipper.一种氧化还原开关分子拉链。
J Am Chem Soc. 2019 Nov 13;141(45):18308-18317. doi: 10.1021/jacs.9b09756. Epub 2019 Oct 29.
5
Reversible Structural Transformation between a Molecular Solomon Link and an Unusual Unsymmetrical Trefoil Knot.分子所罗门环与异常不对称三叶结之间的可逆结构转变
J Am Chem Soc. 2019 Oct 9;141(40):16057-16063. doi: 10.1021/jacs.9b08254. Epub 2019 Sep 25.
6
Fast and Quantitative NMR Metabolite Analysis Afforded by a Paramagnetic Co-Solute.顺磁共溶剂实现的快速定量 NMR 代谢物分析。
Angew Chem Int Ed Engl. 2019 Oct 21;58(43):15283-15286. doi: 10.1002/anie.201908006. Epub 2019 Sep 11.
7
Self-Sorting Assembly of Molecular Trefoil Knots of Single Handedness.单链手性分子三叶纽结的自组装。
J Am Chem Soc. 2019 Sep 11;141(36):14249-14256. doi: 10.1021/jacs.9b06127. Epub 2019 Aug 26.
8
A Potent Halogen-Bonding Donor Motif for Anion Recognition and Anion Template Mechanical Bond Synthesis.一种用于阴离子识别和阴离子模板机械键合成的强效卤素键供体基序。
Angew Chem Int Ed Engl. 2019 Sep 23;58(39):13823-13827. doi: 10.1002/anie.201907625. Epub 2019 Aug 19.
9
Three-Dimensional Protein Structure Determination Using Pseudocontact Shifts of Backbone Amide Protons Generated by Double-Histidine Co-Binding Motifs at Multiple Sites.使用双组氨酸共结合模体在多个位点生成的骨架酰胺质子的赝接触位移来确定三维蛋白质结构。
Biochemistry. 2019 Jul 30;58(30):3243-3250. doi: 10.1021/acs.biochem.9b00404. Epub 2019 Jul 19.
10
Redox active [PdL] cages constructed from rotationally flexible 1,1'-disubstituted ferrocene ligands.由具有旋转灵活性的1,1'-二取代二茂铁配体构建的氧化还原活性[PdL]笼。
Chem Commun (Camb). 2019 Jul 4;55(52):7506-7509. doi: 10.1039/c9cc03321a. Epub 2019 Jun 12.