Solid state nuclear magnetic resonance最新文献

英文中文

J couplings in the solid state from direct energy computations 从直接能量计算中得到固态中的J耦合

IF 3.2 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-12-20 DOI: 10.1016/j.ssnmr.2025.102060

J.W. Zwanziger

引用次数: 0

Impact of Shared Facilities in Advancing Solid-State NMR Research: 2025 Edition 共享设施在推进固态核磁共振研究中的影响：2025年版

IF 3.2 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-11-28 DOI: 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, Moreno Lelli, Anne Lesage, Guido Pintacuda, Miquel Pons, Luís Mafra, José F. Schneider, Gustavo A. Monti, Rodolfo H. Acosta, Horacio M. Pastawski, Brijith Thomas, Yury G. Kolyagin, Vipin Agarwal, Guangjin Hou, Feng Deng, Kai Xue, Takanori Kigawa, G.N. Manjunatha Reddy

引用次数: 0

Resolving 209Bi sites in mixed-halide double perovskites at 28 T 28 T下混合卤化物双钙钛矿中209Bi位的解析

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-11-27 DOI: 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(Cl_1−xBr_x)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.

银铋双钙钛矿是卤化物钙钛矿光电材料的无铅替代品。这些性质可以通过卤化物混合或降维来调整，但要了解这如何改变原子结构，需要一个局部结构探针。铋核磁共振波谱对局部环境极为敏感，但存在严重的四极性展宽。在这里，我们证明了超高场（28.2 T）、快速magic angle自旋（50 kHz）和边带分离脉冲序列的组合可以在混合氯-溴Cs2AgBi(Cl1−xBrx)6（0≤x≤1）双钙钛矿的209Bi NMR谱中区分出所有7种局部[BiX6]构型。在28.2 T下，用超宽谱法测定了Cs2AgBiBr6的81Br核磁共振谱。最后，通过可变场实验（11.7、20.0和28.2 T），确定了低对称性BA4AgBiBr8层状双钙钛矿（BA+ =正丁铵）的209Bi CSA和四极参数。这项工作证明了超高场核磁共振波谱在复杂的当代材料中具有挑战性的核（如209Bi）的前景。

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引用次数: 0

Applications of average Hamiltonian theory to spin polarization transfer in magnetic resonance 平均哈密顿理论在磁共振自旋极化传递中的应用

IF 3.2 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-11-21 DOI: 10.1016/j.ssnmr.2025.102051

Suraj Halder, Shovik Ray, Shubham Kumar Debadatta, Sheetal Kumar Jain

引用次数: 0

Direct polarization transfer to remote nuclei: Expanding the reach of cross-effect Dynamic Nuclear Polarization 直接极化转移到远核：扩展交叉效应动态核极化的范围

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-11-08 DOI: 10.1016/j.ssnmr.2025.102049

Amaria Javed , Ribal Jabbour , Waqqas Zia , Asif Equbal

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

^{1}

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

^{1}

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。

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引用次数: 0

In-situ two-dimensional MAS NMR spectroscopy for heterogeneous catalysis 多相催化的原位二维MAS NMR

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-11-07 DOI: 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.

原位魔角自旋（MAS）核磁共振已成为在原子水平上阐明催化反应机理和催化剂在工作条件下的动态结构演变的关键技术。本文综述了原位MAS NMR在催化反应和催化剂结晶过程研究中的应用，强调了其在实时监测瞬态物质和结构转变方面的独特能力。专业核磁共振硬件（如高温高压（HTHP）转子）和脉冲序列（如快速二维采集）的最新进展显著提高了灵敏度和采集效率，通过原位表征实现了前所未有的机制洞察。我们展示了利用原位MAS NMR技术在催化研究方面的最新突破，包括甲醇转化、沸石合成和表面反应动力学。这篇综述还强调了HTHP原位MAS NMR与快速二维相关光谱的转化集成，特别是对四极核。强调了将硬件（高温高压转子）和软件（脉冲序列）方法相结合在原位MAS NMR开发中的重要性，并讨论了未来方法创新的关键方向。

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引用次数: 0

Transforming solid-state nuclear magnetic resonance towards a chemistry-ready technique 将固态核磁共振转变为化学准备技术

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-10-30 DOI: 10.1016/j.ssnmr.2025.102048

Raphaële Coulon , David Gajan , Wassilios Papawassiliou , Andrew J. Pell , Judith Schlagnitweit , Franck Fayon , Pierre Florian , Dominique Massiot , Armin Afrough , Dennis W. Juhl , Thomas Vosegaard , Linda Cerofolini , Moreno Lelli , Massimo Lucci , Claudio Luchinat , Ruud L.E.G. Aspers , Jennifer S. Gómez , Arno P.M. Kentgens , Sander F.H. Lambregts , Y.T. Angel Wong , Anne Lesage

Solid-state nuclear magnetic resonance (solid-state NMR) is an essential tool for probing local structure and dynamics in complex materials, yet its uptake in the broader chemistry community has remained limited by technical and operational barriers. The PANACEA project established a pan-European infrastructure to transform solid-state NMR into a community-ready analytical technique by combining state-of-the-art instrumentation, coordinated user access, and targeted technological innovation. Over three years, PANACEA enabled over 90 user projects across chemistry and materials science, while driving advances in DNP methods, probe design, ultra-fast MAS, and interoperable software platforms such as EasyNMR and CHEMeDATA. This article presents the main outcomes of the initiative, illustrating how infrastructure-driven research and guided access can broaden the impact of solid-state NMR and integrate it into mainstream chemical workflows.

固态核磁共振（Solid-state NMR）是探测复杂材料局部结构和动力学的重要工具，但其在更广泛的化学领域的应用仍然受到技术和操作障碍的限制。PANACEA项目建立了一个泛欧洲基础设施，通过结合最先进的仪器、协调的用户访问和有针对性的技术创新，将固态核磁共振转化为一种社区就绪的分析技术。三年来，PANACEA在化学和材料科学领域支持了90多个用户项目，同时推动了DNP方法、探针设计、超快速MAS和EasyNMR和CHEMeDATA等可互操作软件平台的进步。本文介绍了该计划的主要成果，说明了基础设施驱动的研究和指导访问如何扩大固态核磁共振的影响，并将其整合到主流化学工作流程中。

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引用次数: 0

Hyperfine interactions and magnetic order in oxyborate Co3BO5 according to 10,11B and 59Co NMR data 根据10、11B和59Co核磁共振数据，氧硼酸盐Co3BO5的超精细相互作用和磁序。

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-10-11 DOI: 10.1016/j.ssnmr.2025.102047

A.G. Smolnikov , M.E. Kashnikova , N.A. Utkin , A.F. Sadykov , Yu.V. Piskunov , V.V. Ogloblichev , A.P. Gerashenko , L.A. Stashkova , N.V. Kazak

Information on the local charge and magnetic environment of ^10,11B and ⁵⁹Co nuclei in homometallic oxyborate Co₃BO₅ has been obtained using NMR spectroscopy. The data were obtained over a wide range of temperatures, in both paramagnetic and magnetically ordered states of the sample, as well as in various magnetic fields. The parameters of the electric field gradient tensor and the values hyperfine fields at the positions of the studied nuclei have been experimentally determined, which is possible only by NMR methods. The data indicate the presence of super-superexchange Co – O – B – O – Co interactions, which presumably occur with the participation of sp²-hybridized orbitals of the B³⁺ ion. A model of super-superexchange involving orbitals of the Co³⁺ ion in the low-spin (LS) 3 d⁶ state is proposed. The ⁵⁹Co NMR data in the magnetically ordered phase most likely relate to cobalt ions in the LS state with local fields of 31.5 (3) kOe induced on the nuclei. Based on NMR data from ^10,11B and ⁵⁹Co, a magnetic order model is proposed in which the magnetic moments of cobalt ions are directed predominantly along the b axis of the crystal.

利用核磁共振波谱法获得了同金属氧化硼酸盐Co3BO5中10、11B和59Co核的局部电荷和磁环境信息。这些数据是在很宽的温度范围内获得的，在样品的顺磁性和磁性有序状态下，以及在不同的磁场中。电场梯度张量的参数和所研究的原子核位置的超精细场的值已经通过实验确定，这只有通过核磁共振方法才能实现。数据表明存在超交换Co - O - B - O - Co相互作用，这可能是在B3+离子的sp2杂化轨道参与下发生的。提出了低自旋（LS） 3d6态Co3+离子轨道的超超交换模型。磁有序相的59Co核磁共振数据很可能与LS态的钴离子有关，在核上诱导出31.5 (3)kOe的局部场。基于10、11B和59Co的核磁共振数据，提出了钴离子磁矩主要沿晶体b轴方向的磁序模型。

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引用次数: 0

Measurement of C-H distances in solids at natural abundance via proton-detected fast MAS NMR spectroscopy. 通过质子检测快速MAS核磁共振波谱法测量固体中天然丰度的碳氢距离。

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-10-01 Epub Date: 2025-08-06 DOI: 10.1016/j.ssnmr.2025.102031

Yayatika Bhardwaj, Ketan Kumar Rohilla, Yusuke Nishiyama, Manoj Kumar Pandey

Measurement of heteronuclear distances from the radio-frequency (rf) pulse-based recoupling of NMR experiments is vital for structural refinement and dynamics studies at the atomic level. Despite advancements in the design and development of recoupling methods, the extraction of the directly-bonded heteronuclear XH distances in samples with XH₂ moieties remains challenging. This is primarily due to the interference effects from the neighboring spins/local fields leading to distorted dipolar coupling powder lineshapes. In this regard, we present a proton-detected 3D ¹³C chemical shift (CS)/¹³C-¹H dipolar coupling/¹H chemical shift (CS) correlation experiment under fast magic angle spinning (MAS), which has the potential to measure the directly-bonded CH distances in naturally abundant samples with CH₂ groups. We have implemented the windowless ROCSA-based ¹³C-¹H dipolar interaction recoupling scheme under ¹H evolution to achieve undistorted ¹³C-¹H dipolar coupling powder lineshapes in contrast to our previously reported windowless ROCSA-DIPSHIFT method under X-nuclei evolution, wherein extraction of the directly-bonded CH distances in samples with CH₂ groups is shown to be sensitive to the presence of the local fields due to neighboring spins. ¹³C-¹H distances reported from the method presented in this work are also validated from the results emerging from the quantum chemical calculations.

从基于射频（rf）脉冲的核磁共振实验中测量异核距离对于原子水平上的结构改进和动力学研究至关重要。尽管在设计和开发重偶联方法方面取得了进展，但从含有XH2基团的样品中提取直接键合的异核XH距离仍然具有挑战性。这主要是由于邻近自旋/局部场的干涉效应导致偶极耦合粉末线形状扭曲。为此，我们提出了快速魔角旋转（MAS）下质子检测的3D 13C化学位移(CS)/13C-1H偶极耦合/1H化学位移（CS）相关实验，该实验有可能测量天然丰富的含CH2基团样品中的直接键合CH距离。我们在1H演化下实现了基于无窗口rocsa的13C-1H偶极相互作用重耦合方案，以获得不扭曲的13C-1H偶极耦合粉末线形状，与我们之前报道的x核演化下无窗口ROCSA-DIPSHIFT方法相反，其中提取具有CH2基团的样品中的直接键合CH距离被证明对邻近自旋引起的局部场的存在很敏感。从本工作中提出的方法中报告的13C-1H距离也从量子化学计算的结果中得到验证。

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引用次数: 0

Through-space NMR correlations between two different half-integer quadrupolar nuclei using T-HMQC sequences 利用T-HMQC序列研究两个不同的半整数四极核之间的空间核磁共振相关性。

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Solid state nuclear magnetic resonance

Pub Date : 2025-09-09 DOI: 10.1016/j.ssnmr.2025.102044

Yury G. Kolyagin , Julien Trébosc , Olivier Lafon , Jean-Paul Amoureux

Proximities between spin-1/2, e.g. ¹H and ¹³C, and quadrupolar nuclei can be analyzed using HMQC (Heteronuclear Multiple-Quantum Correlation) experiments, in which two continuous-wave irradiations similar to those used in TRAPDOR (TRAnsfer of Population in DOuble-Resonance) experiments are applied on the indirectly detected quadrupolar isotope during the defocusing and refocusing delays. Here, we demonstrate that this sequence, called T-HMQC (T stands for TRAPDOR), can be applied to probe proximities between distinct half-integer spin quadrupolar isotopes. We introduce two novel variants of this sequence to reduce the number of resonances along the indirect dimension. These selective variants employ either (i) an echo-antiecho quadrature detection to only retain the single-quantum (1Q) coherences or (ii) two π-pulses selective of the central-transition (CT) to observe only the 1Q-CT coherences. We analyze how the effects of various experimental parameters, including the synchronization of the TRAPDOR recoupling pulses with the sample rotation, and their radio-frequency (rf) field amplitude and frequency offset, affect the efficiency of ¹¹B-²⁷Al T-HMQC experiments on a magnesium aluminoborate glass. The performances of these T-HMQC sequences are compared to those of the D-HMQC scheme employing the SPI-R³ (Synchronous Phase-Inversion Rotary-Resonance-Recoupling) or REDOR (Rotational-Echo DOuble-Resonance) symmetry-based heteronuclear dipolar recouplings built from CT-selective pulses. We demonstrate that the two TRAPDOR pulses in the T-HMQC sequence must be separated by an integer number of rotor periods and must employ the maximum rf field strength compatible with the probe specifications. Furthermore, as the TRAPDOR pulses distribute the populations equally to all possible coherences, the sensitivity of the T-HMQC selective variants is lower than that of the D-HMQC techniques. To limit this sensitivity decrease and the number of cross-peaks, it is preferable to detect indirectly the quadrupolar nucleus I with the lowest spin number, and in the case of I = 3/2, the resolution along the indirect dimension can be enhanced with respect to a MAS spectrum (for instance, by a factor of 27/7, without taking into account the quadrupolar-induced shift (QIS), through the sole indirect detection of triple-quantum (3Q) coherences). Moreover, owing to the use of a high-power TRAPDOR recoupling, the T-HMQC technique benefits from a wider excitation bandwidth than the D-HMQC methods, which is advantageous for broad NMR spectra, especially at high magnetic fields.

利用HMQC （Heteronuclear multiquantum Correlation）实验，可以分析自旋1/2（例如1H和13C）与四极核之间的接近度。在HMQC （Heteronuclear multiquantum Correlation）实验中，在离焦和重焦延迟期间，对间接检测到的四极同位素进行两次类似于TRAPDOR （DOuble-Resonance中种群转移）实验的连续波照射。在这里，我们证明了这个序列，称为T- hmqc (T代表TRAPDOR)，可以应用于探测不同的半整数自旋四极同位素之间的接近度。我们引入了该序列的两个新变体，以减少沿间接维度的共振数量。这些选择性变体要么采用(i)回波-反回波正交检测，仅保留单量子（1Q）相干性，要么采用（ii）双π脉冲选择性中央跃迁（CT），仅观察1Q-CT相干性。我们分析了不同实验参数对11B-27Al T-HMQC在硼酸铝镁玻璃上实验效率的影响，包括TRAPDOR重耦合脉冲与样品旋转的同步，以及它们的射频场振幅和频率偏移。将这些T-HMQC序列的性能与采用同步相位反转旋转共振重耦合（SPI-R3）或旋转回声双共振（REDOR）对称的基于ct选择脉冲的异核偶极重耦合的D-HMQC方案进行了比较。我们证明了T-HMQC序列中的两个TRAPDOR脉冲必须由整数转子周期分开，并且必须采用与探头规格兼容的最大射频场强度。此外，由于TRAPDOR脉冲将种群均匀地分布到所有可能的相干中，T-HMQC选择变体的灵敏度低于D-HMQC技术。为了限制这种灵敏度下降和交叉峰的数量，最好是间接检测具有最低自旋数的四极核I，并且在I = 3/2的情况下，相对于MAS光谱，沿间接维度的分辨率可以提高（例如，通过唯一间接检测三量子（3Q）相干，不考虑四极诱导位移（QIS），通过27/7的因子）。此外，由于使用了高功率TRAPDOR耦合，T-HMQC技术比D-HMQC方法受益于更宽的激励带宽，这有利于更宽的核磁共振波谱，特别是在高磁场下。

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