Pub Date : 2026-02-09DOI: 10.1016/j.ssnmr.2026.102072
Brijith Thomas, G.N. Manjunatha Reddy
{"title":"Editorial: Emerging Concepts and Applications in Solid-State NMR Spectroscopy","authors":"Brijith Thomas, G.N. Manjunatha Reddy","doi":"10.1016/j.ssnmr.2026.102072","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2026.102072","url":null,"abstract":"","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"59 1","pages":""},"PeriodicalIF":3.2,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-07DOI: 10.1016/j.ssnmr.2026.102071
Sojung Seo, Sunghee Min, Sangdoo Ahn, Young Joo Lee
{"title":"NMR study of electrolytes for Li rechargeable batteries: from liquid to solid electrolytes","authors":"Sojung Seo, Sunghee Min, Sangdoo Ahn, Young Joo Lee","doi":"10.1016/j.ssnmr.2026.102071","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2026.102071","url":null,"abstract":"","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"3 1","pages":""},"PeriodicalIF":3.2,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-03DOI: 10.1016/j.ssnmr.2026.102070
Austin Peach, Nicolas Fabregue, David Gajan, Frédéric Mentink-Vigier, Faith Scott, Christel Gervais, Danielle Laurencin
{"title":"Corrigendum to “Experimental and computational 17O solid-state NMR investigation of Na- and K-(bi)carbonate salts” [Solid State Nucl. Magn. Reson. 139 (2025) 102020]","authors":"Austin Peach, Nicolas Fabregue, David Gajan, Frédéric Mentink-Vigier, Faith Scott, Christel Gervais, Danielle Laurencin","doi":"10.1016/j.ssnmr.2026.102070","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2026.102070","url":null,"abstract":"","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"63 1","pages":""},"PeriodicalIF":3.2,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-26DOI: 10.1016/j.ssnmr.2025.102061
Ziyao Peng , Xiaolin Wang , Victor Terskikh , Ivan Hung , Zhehong Gan , Gang Wu
Quadrupole central transition (QCT) NMR has recently been shown to be an effective way of obtaining high spectral resolution for half-integer quadrupolar nuclei in slowly tumbling molecules in liquids. QCT NMR for slowly tumbling molecules shares many common characteristics with conventional CT-based solid-state NMR for half-integer quadrupolar nuclei. As a result, QCT NMR can be considered to be a cousin of solid-state NMR. Experimental QCT NMR data reported so far in the literature strongly indicate that the optimal resolution achievable in QCT NMR increases with the strength of the applied magnetic field (B0). In this study, we showed that, if the nuclear quadrupole interaction is the predominant relaxation mechanism, the minimal line width (expressed in ppm) obtained in QCT NMR is proportional to B0−3. In comparison, the corresponding field dependence in CT-based solid-state NMR is only B0−2. We also demonstrated that the presence of shielding anisotropy (SA) would significantly reduce the B0−3 dependence in QCT NMR. We presented new 17O (I = 5/2) QCT NMR results obtained at multiple magnetic fields up to 35.2 T and carefully examined a wide range of previously reported QCT NMR data from the literature for 27Al (I = 5/2), 39K (I = 3/2), 45Sc (I = 7/2), 59Co (I = 7/2), 71Ga (I = 3/2), and 87Rb (I = 3/2) nuclei. Our findings provide a general guideline for future QCT NMR applications especially at ultrahigh magnetic fields.
近年来，四极中心跃迁核磁共振（QCT）已被证明是获得液体中缓慢翻滚分子中半整数四极核的高光谱分辨率的有效方法。慢滚分子的QCT核磁共振与传统的基于ct的固态核磁共振具有许多共同特征。因此，QCT核磁共振可以被认为是固态核磁共振的表亲。目前文献报道的实验QCT核磁共振数据强烈表明，QCT核磁共振可达到的最佳分辨率随着外加磁场强度的增加而增加（B0）。在本研究中，我们发现，如果核四极相互作用是主要的弛豫机制，那么在QCT NMR中获得的最小线宽（以ppm表示）与B0−3成正比。相比之下，基于ct的固态核磁共振对应的场依赖仅为B0−2。我们还证明了屏蔽各向异性（SA）的存在会显著降低QCT核磁共振中B0−3的依赖性。我们提出了在高达35.2 T的多个磁场下获得的新的17O (I = 5/2) QCT核磁共振结果，并仔细检查了文献中广泛的先前报道的27Al (I = 5/2), 39K (I = 3/2), 45Sc (I = 7/2), 59Co (I = 7/2), 71Ga （I = 3/2）和87Rb （I = 3/2）核的QCT核磁共振数据。我们的发现为未来的QCT核磁共振应用，特别是在超高磁场下的应用提供了一般指导。
{"title":"On the optimal spectral resolution in quadrupole central transition NMR at ultrahigh magnetic fields","authors":"Ziyao Peng , Xiaolin Wang , Victor Terskikh , Ivan Hung , Zhehong Gan , Gang Wu","doi":"10.1016/j.ssnmr.2025.102061","DOIUrl":"10.1016/j.ssnmr.2025.102061","url":null,"abstract":"<div><div>Quadrupole central transition (QCT) NMR has recently been shown to be an effective way of obtaining high spectral resolution for half-integer quadrupolar nuclei in slowly tumbling molecules in liquids. QCT NMR for slowly tumbling molecules shares many common characteristics with conventional CT-based solid-state NMR for half-integer quadrupolar nuclei. As a result, QCT NMR can be considered to be a cousin of solid-state NMR. Experimental QCT NMR data reported so far in the literature strongly indicate that the optimal resolution achievable in QCT NMR increases with the strength of the applied magnetic field (<em>B</em><sub>0</sub>). In this study, we showed that, if the nuclear quadrupole interaction is the predominant relaxation mechanism, the minimal line width (expressed in ppm) obtained in QCT NMR is proportional to <em>B</em><sub>0</sub><sup>−3</sup>. In comparison, the corresponding field dependence in CT-based solid-state NMR is only <em>B</em><sub>0</sub><sup>−2</sup>. We also demonstrated that the presence of shielding anisotropy (SA) would significantly reduce the <em>B</em><sub>0</sub><sup>−3</sup> dependence in QCT NMR. We presented new <sup>17</sup>O (<em>I</em> = 5/2) QCT NMR results obtained at multiple magnetic fields up to 35.2 T and carefully examined a wide range of previously reported QCT NMR data from the literature for <sup>27</sup>Al (<em>I</em> = 5/2), <sup>39</sup>K (<em>I</em> = 3/2), <sup>45</sup>Sc (<em>I</em> = 7/2), <sup>59</sup>Co (<em>I</em> = 7/2), <sup>71</sup>Ga (<em>I</em> = 3/2), and <sup>87</sup>Rb (<em>I</em> = 3/2) nuclei. Our findings provide a general guideline for future QCT NMR applications especially at ultrahigh magnetic fields.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"141 ","pages":"Article 102061"},"PeriodicalIF":2.4,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145840527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-20DOI: 10.1016/j.ssnmr.2025.102060
J.W. Zwanziger
A simple method for computing couplings from first principles is proposed, implemented, and tested. In this approach the coupling, which is just the mixed second derivative of the energy with respect to two nuclear magnetic dipoles, is evaluated non-perturbatively by computing the total energy with different fixed dipoles of various orientations, combined in a finite difference scheme. The approach is equally applicable to molecules and solids. Details of the implementation are presented, and a variety of examples in molecules and solids are provided.
{"title":"J couplings in the solid state from direct energy computations","authors":"J.W. Zwanziger","doi":"10.1016/j.ssnmr.2025.102060","DOIUrl":"10.1016/j.ssnmr.2025.102060","url":null,"abstract":"<div><div>A simple method for computing <span><math><mi>J</mi></math></span> couplings from first principles is proposed, implemented, and tested. In this approach the coupling, which is just the mixed second derivative of the energy with respect to two nuclear magnetic dipoles, is evaluated non-perturbatively by computing the total energy with different fixed dipoles of various orientations, combined in a finite difference scheme. The approach is equally applicable to molecules and solids. Details of the implementation are presented, and a variety of examples in molecules and solids are provided.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"141 ","pages":"Article 102060"},"PeriodicalIF":2.4,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.ssnmr.2025.102053
Robert W. Schurko , Chad M. Rienstra , Christopher P. Jaroniec , Alexandar L. Hansen , W. Trent Franks , David L. Bryce , Andreas Brinkmann , Victor Terskikh , Steven P. Brown , Dinu Iuga , Carine van Heijenoort , Franck Fayon , Sylvain Bertaina , Carlos Alfonso , Göran Karlsson , Gerhard Gröbner , Marek J. Potrzebowski , Linda Cerofolini , Enrico Ravera , Marco Fragai , G.N. Manjunatha Reddy
Shared research facilities (SRFs) offer researchers cost-effective access to advanced analytical instrumentation that individual laboratories may find challenging to acquire or maintain. By centralizing resources, SRFs support a diverse user community including students, early-career scientists, senior principal investigators, and industrial collaborators, while providing expert technical support and ensuring efficient use of infrastructure and funding. These facilities not only drive research productivity and foster interdisciplinary collaboration, but also serve as centers for training the next generation of scientists. In this article, SRFs that offer solid-state nuclear magnetic resonance (NMR) capabilities are discussed, highlighting representative examples, their accessibility, governance models, technical operations, application areas, and data-sharing practices. Usage data reveal that solid-state NMR-based SRFs strongly align with high-priority research goals, contributing to impactful projects across chemistry, life sciences, and materials science, as reflected in publication outcomes. The article also emphasizes that the collaborative networks among SRFs enhance knowledge exchange and resource coordination. Such coordinated inter-facility partnerships are expected to address emerging challenges, ultimately supporting sustainable infrastructure that meets the evolving needs of the solid-state NMR community.
{"title":"Impact of shared facilities in advancing solid-state NMR research: 2025 edition","authors":"Robert W. Schurko , Chad M. Rienstra , Christopher P. Jaroniec , Alexandar L. Hansen , W. Trent Franks , David L. Bryce , Andreas Brinkmann , Victor Terskikh , Steven P. Brown , Dinu Iuga , Carine van Heijenoort , Franck Fayon , Sylvain Bertaina , Carlos Alfonso , Göran Karlsson , Gerhard Gröbner , Marek J. Potrzebowski , Linda Cerofolini , Enrico Ravera , Marco Fragai , G.N. Manjunatha Reddy","doi":"10.1016/j.ssnmr.2025.102053","DOIUrl":"10.1016/j.ssnmr.2025.102053","url":null,"abstract":"<div><div>Shared research facilities (SRFs) offer researchers cost-effective access to advanced analytical instrumentation that individual laboratories may find challenging to acquire or maintain. By centralizing resources, SRFs support a diverse user community including students, early-career scientists, senior principal investigators, and industrial collaborators, while providing expert technical support and ensuring efficient use of infrastructure and funding. These facilities not only drive research productivity and foster interdisciplinary collaboration, but also serve as centers for training the next generation of scientists. In this article, SRFs that offer solid-state nuclear magnetic resonance (NMR) capabilities are discussed, highlighting representative examples, their accessibility, governance models, technical operations, application areas, and data-sharing practices. Usage data reveal that solid-state NMR-based SRFs strongly align with high-priority research goals, contributing to impactful projects across chemistry, life sciences, and materials science, as reflected in publication outcomes. The article also emphasizes that the collaborative networks among SRFs enhance knowledge exchange and resource coordination. Such coordinated inter-facility partnerships are expected to address emerging challenges, ultimately supporting sustainable infrastructure that meets the evolving needs of the solid-state NMR community.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"141 ","pages":"Article 102053"},"PeriodicalIF":2.4,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-27DOI: 10.1016/j.ssnmr.2025.102052
Alexandre J.D. Pauletto, Ryan J. Bragg, Richard I. Walton, Michael A. Hope
Ag–Bi double perovskites are of interest as lead-free alternatives to halide perovskite optoelectronic materials. The properties can be tuned by halide mixing or dimensional reduction, but to understand how this changes the atomic structure requires a local structural probe. 209Bi NMR spectroscopy is extremely sensitive to the local environment but suffers from severe quadrupolar broadening. Here, we show that the combination of ultra-high field (28.2 T), fast magic angle spinning (50 kHz), and a sideband separation pulse sequence enables all seven local [BiX6] configurations to be distinguished in the 209Bi NMR spectra of mixed chloride–bromide Cs2AgBi(Cl1−xBrx)6 (0 ≤ x ≤ 1) double perovskites. The 81Br NMR spectrum of Cs2AgBiBr6 was further measured at 28.2 T using ultra-wideline methods. Finally, variable field experiments (11.7, 20.0, and 28.2 T) enabled the 209Bi CSA and quadrupolar parameters to be determined for the lower symmetry BA4AgBiBr8 layered double perovskite (BA+ = n-butylammonium). This work demonstrates the promise of ultra-high field NMR spectroscopy for challenging nuclei such as 209Bi in complex contemporary materials.
{"title":"Resolving 209Bi sites in mixed-halide double perovskites at 28 T","authors":"Alexandre J.D. Pauletto, Ryan J. Bragg, Richard I. Walton, Michael A. Hope","doi":"10.1016/j.ssnmr.2025.102052","DOIUrl":"10.1016/j.ssnmr.2025.102052","url":null,"abstract":"<div><div>Ag–Bi double perovskites are of interest as lead-free alternatives to halide perovskite optoelectronic materials. The properties can be tuned by halide mixing or dimensional reduction, but to understand how this changes the atomic structure requires a local structural probe. <sup>209</sup>Bi NMR spectroscopy is extremely sensitive to the local environment but suffers from severe quadrupolar broadening. Here, we show that the combination of ultra-high field (28.2 T), fast magic angle spinning (50 kHz), and a sideband separation pulse sequence enables all seven local [BiX<sub>6</sub>] configurations to be distinguished in the <sup>209</sup>Bi NMR spectra of mixed chloride–bromide Cs<sub>2</sub>AgBi(Cl<sub>1−<em>x</em></sub>Br<sub><em>x</em></sub>)<sub>6</sub> (0 ≤ <em>x</em> ≤ 1) double perovskites. The <sup>81</sup>Br NMR spectrum of Cs<sub>2</sub>AgBiBr<sub>6</sub> was further measured at 28.2 T using ultra-wideline methods. Finally, variable field experiments (11.7, 20.0, and 28.2 T) enabled the <sup>209</sup>Bi CSA and quadrupolar parameters to be determined for the lower symmetry BA<sub>4</sub>AgBiBr<sub>8</sub> layered double perovskite (BA<sup>+</sup> = <em>n</em>-butylammonium). This work demonstrates the promise of ultra-high field NMR spectroscopy for challenging nuclei such as <sup>209</sup>Bi in complex contemporary materials.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"141 ","pages":"Article 102052"},"PeriodicalIF":2.4,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Average Hamiltonian Theory (AHT) is a widely used framework for analyzing spin dynamics in magnetic resonance experiments. The application of radiofrequency or microwave pulses, together with sample spinning, renders the Hamiltonian explicitly time-dependent, complicating the description of spin-state evolution. AHT overcomes this challenge by employing the Magnus expansion to generate a time-independent effective Hamiltonian. In this review, we discuss applications of AHT to spin polarization transfer mechanisms in nucleus–nucleus, electron–nucleus, and electron–electron–nucleus spin systems. AHT analysis to obtain an effective Hamiltonian in an appropriate interaction frame followed by density matrix evolution reveals optimal conditions for polarization transfer. The expression of the final density matrix also provides insight into the efficiency of the polarization transfer mechanism and their dependencies on external as well as internal interactions. Such analysis guides the design of experimental protocols, enabling informed choices of field strength, irradiation frequency, and pulse schemes to enhance nuclear polarization and dynamic nuclear polarization (DNP) efficiency. Thus, AHT serves as a powerful tool for both interpreting and optimizing polarization transfer experiments.
{"title":"Applications of Average Hamiltonian Theory to spin polarization transfer in magnetic resonance","authors":"Suraj Halder, Shovik Ray , Shubham Kumar Debadatta , Sheetal Kumar Jain","doi":"10.1016/j.ssnmr.2025.102051","DOIUrl":"10.1016/j.ssnmr.2025.102051","url":null,"abstract":"<div><div>Average Hamiltonian Theory (AHT) is a widely used framework for analyzing spin dynamics in magnetic resonance experiments. The application of radiofrequency or microwave pulses, together with sample spinning, renders the Hamiltonian explicitly time-dependent, complicating the description of spin-state evolution. AHT overcomes this challenge by employing the Magnus expansion to generate a time-independent effective Hamiltonian. In this review, we discuss applications of AHT to spin polarization transfer mechanisms in nucleus–nucleus, electron–nucleus, and electron–electron–nucleus spin systems. AHT analysis to obtain an effective Hamiltonian in an appropriate interaction frame followed by density matrix evolution reveals optimal conditions for polarization transfer. The expression of the final density matrix also provides insight into the efficiency of the polarization transfer mechanism and their dependencies on external as well as internal interactions. Such analysis guides the design of experimental protocols, enabling informed choices of field strength, irradiation frequency, and pulse schemes to enhance nuclear polarization and dynamic nuclear polarization (DNP) efficiency. Thus, AHT serves as a powerful tool for both interpreting and optimizing polarization transfer experiments.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"141 ","pages":"Article 102051"},"PeriodicalIF":2.4,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145567208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dynamic Nuclear Polarization (DNP) has revolutionized the field of solid-state NMR spectroscopy by significantly improving the sensitivity of nuclear magnetic resonance experiments. Conventionally, cross-effect DNP relies on biradicals to transfer polarization from coupled electron spins to nearby nuclear spins and subsequent relay to target nuclei via a spin diffusion mechanism. However, direct transfer of electron spin polarization to distant nuclei remains a significant challenge due to the small magnitude of effective Hamiltonian, limiting applicability of DNP in various contexts. In this work, we investigate a biradical design concept that involves a very strong electron–electron coupling, with a magnitude of hundreds of MHz, which could enable direct polarization transfer from coupled electron spins to nuclear spins over much longer distances, exceeding 2.0 nm. The concept is experimentally supported using a 14.1 T MAS DNP setup for various nuclei. The use of ASYMPOL-POK, a strongly coupled biradical, results in up to a four-fold increase in long-range H DNP enhancement compared to AMUPOL, a commonly used standard polarizing agent in traditional MAS DNP.
We also discuss the potential of tailored biradicals in scenarios where conventional spin diffusion mechanisms are inefficient or where direct nuclear spin polarization enhancement or sensing through electron spin interactions is desired. Our study presents an avenue for expanding the scope of cross-effect DNP in solid-state NMR spectroscopy of H, 19F and 31P nuclei, commonly found in various biological and material systems.
动态核极化（DNP）通过显著提高核磁共振实验的灵敏度，彻底改变了固态核磁共振波谱学领域。传统上，交叉效应DNP依赖于双基将极化从耦合电子自旋转移到附近的核自旋，然后通过自旋扩散机制传递到目标核。然而，由于有效哈密顿量较小，电子自旋极化直接转移到远核仍然是一个重大挑战，限制了DNP在各种情况下的适用性。在这项工作中，我们研究了一种双基设计概念，它涉及到一个非常强的电子-电子耦合，其量级为数百MHz，可以实现从耦合电子自旋到核自旋的直接极化转移，距离超过2.0 nm。用14.1 T MAS DNP装置对各种核进行了实验支持。与传统MAS DNP中常用的标准极化剂AMUPOL相比，使用强耦合双自由基ASYMPOL-POK，远程1H DNP增强效果可提高4倍。我们还讨论了定制双基在传统自旋扩散机制效率低下或需要通过电子自旋相互作用直接增强核自旋极化或传感的情况下的潜力。我们的研究为扩大交叉效应DNP在各种生物和材料系统中常见的1H， 19F和31P核的固态核磁共振波谱中的范围提供了一条途径。
{"title":"Direct polarization transfer to remote nuclei: Expanding the reach of cross-effect Dynamic Nuclear Polarization","authors":"Amaria Javed , Ribal Jabbour , Waqqas Zia , Asif Equbal","doi":"10.1016/j.ssnmr.2025.102049","DOIUrl":"10.1016/j.ssnmr.2025.102049","url":null,"abstract":"<div><div>Dynamic Nuclear Polarization (DNP) has revolutionized the field of solid-state NMR spectroscopy by significantly improving the sensitivity of nuclear magnetic resonance experiments. Conventionally, cross-effect DNP relies on biradicals to transfer polarization from coupled electron spins to nearby nuclear spins and subsequent relay to target nuclei via a spin diffusion mechanism. However, direct transfer of electron spin polarization to distant nuclei remains a significant challenge due to the small magnitude of effective Hamiltonian, limiting applicability of DNP in various contexts. In this work, we investigate a biradical design concept that involves a very strong electron–electron coupling, with a magnitude of hundreds of MHz, which could enable direct polarization transfer from coupled electron spins to nuclear spins over much longer distances, exceeding 2.0 nm. The concept is experimentally supported using a 14.1 T MAS DNP setup for various nuclei. The use of ASYMPOL-POK, a strongly coupled biradical, results in up to a four-fold increase in long-range <span><math><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup></math></span>H DNP enhancement compared to AMUPOL, a commonly used standard polarizing agent in traditional MAS DNP.</div><div>We also discuss the potential of tailored biradicals in scenarios where conventional spin diffusion mechanisms are inefficient or where direct nuclear spin polarization enhancement or sensing through electron spin interactions is desired. Our study presents an avenue for expanding the scope of cross-effect DNP in solid-state NMR spectroscopy of <span><math><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup></math></span>H, <sup>19</sup>F and <sup>31</sup>P nuclei, commonly found in various biological and material systems.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"140 ","pages":"Article 102049"},"PeriodicalIF":2.4,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145461884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-07DOI: 10.1016/j.ssnmr.2025.102050
Lixin Liang , Daoning Wu , Guangjin Hou
In-situ magic-angle spinning (MAS) NMR has emerged as a pivotal technique for elucidating catalytic reaction mechanisms and dynamic structural evolution of catalysts at the atomic level under working conditions. This review summarizes the applications of in-situ MAS NMR in the investigation of catalytic reactions and crystallization processes of catalysts, highlighting its unique capability in real-time monitoring of transient species and structural transformations. Recent advances in specialized NMR hardware (e.g., high-temperature and high-pressure (HTHP) rotors) and pulse sequences (e.g., fast 2D acquisition) have significantly enhanced the sensitivity and acquisition efficiency, enabling unprecedented mechanistic insights via in-situ charactorization. We showcase the latest breakthroughs in catalysis research utilizing in-situ MAS NMR spectroscopy, including methanol conversion, zeolite synthesis, and surface reaction dynamics. This review also emphasizes the transformative integration of HTHP in-situ MAS NMR with fast 2D correlation spectroscopy particularly for quadrupolar nuclei. The importance of combining the hardware (HTHP rotors) and software (pulse sequences) methods is highlighted in developing in-situ MAS NMR, and the key directions for future methodological innovations are discussed.
{"title":"In-situ two-dimensional MAS NMR spectroscopy for heterogeneous catalysis","authors":"Lixin Liang , Daoning Wu , Guangjin Hou","doi":"10.1016/j.ssnmr.2025.102050","DOIUrl":"10.1016/j.ssnmr.2025.102050","url":null,"abstract":"<div><div><em>In-situ</em> magic-angle spinning (MAS) NMR has emerged as a pivotal technique for elucidating catalytic reaction mechanisms and dynamic structural evolution of catalysts at the atomic level under working conditions. This review summarizes the applications of <em>in-situ</em> MAS NMR in the investigation of catalytic reactions and crystallization processes of catalysts, highlighting its unique capability in real-time monitoring of transient species and structural transformations. Recent advances in specialized NMR hardware (e.g., high-temperature and high-pressure (HTHP) rotors) and pulse sequences (e.g., fast 2D acquisition) have significantly enhanced the sensitivity and acquisition efficiency, enabling unprecedented mechanistic insights via <em>in-situ</em> charactorization. We showcase the latest breakthroughs in catalysis research utilizing <em>in-situ</em> MAS NMR spectroscopy, including methanol conversion, zeolite synthesis, and surface reaction dynamics. This review also emphasizes the transformative integration of HTHP <em>in-situ</em> MAS NMR with fast 2D correlation spectroscopy particularly for quadrupolar nuclei. The importance of combining the hardware (HTHP rotors) and software (pulse sequences) methods is highlighted in developing <em>in-situ</em> MAS NMR, and the key directions for future methodological innovations are discussed.</div></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"140 ","pages":"Article 102050"},"PeriodicalIF":2.4,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号