Solid state nuclear magnetic resonance最新文献

{"title":"Improved resolution for spin-3/2 isotopes in solids via the indirect NMR detection of triple-quantum coherences using the T-HMQC sequence","authors":"Racha Bayzou ,&nbsp;Julien Trébosc ,&nbsp;Ivan Hung ,&nbsp;Zhehong Gan ,&nbsp;Andrew Rankin ,&nbsp;Olivier Lafon ,&nbsp;Jean-Paul Amoureux","doi":"10.1016/j.ssnmr.2022.101835","DOIUrl":"10.1016/j.ssnmr.2022.101835","url":null,"abstract":"<div><p><span>The indirect NMR detection of quadrupolar nuclei<span> in solids under magic-angle spinning (MAS) is possible with the through-space HMQC (heteronuclear multiple-quantum coherence) scheme incorporating the TRAPDOR (transfer of population in double-resonance) dipolar recoupling. This sequence, called T-HMQC, exhibits limited </span></span><em>t</em>₁-noise. In this contribution, with the help of numerical simulations of spin dynamics, we show that most of the time, the fastest coherence transfer in the T-HMQC scheme is achieved when TRAPDOR recoupling employs the highest radiofrequency (rf) field compatible with the probe specifications. We also demonstrate how the indirect detection of the triple-quantum (3Q) coherences of spin-3/2 quadrupolar nuclei in solids improves the spectral resolution for these isotopes. The sequence is then called T-HMQC₃. We demonstrate the gain in resolution provided by this sequence for the indirect proton detection of ³⁵Cl nuclei in <span>l</span>-histidine∙HCl and <span>l</span>-cysteine∙HCl, as well as that of ²³Na isotope in NaH₂PO₄. These experiments indicate that the gain in resolution depends on the relative values of the chemical and quadrupolar-induced shifts (QIS) for the different spin-3/2 species. In the case of NaH₂PO₄, we show that the transfer efficiency of the T-HMQC₃ sequence employing an rf-field of 80 kHz with a MAS frequency of 62.5 kHz reaches 75% of that of the <em>t</em>₁-noise eliminated (TONE) dipolar-mediated HMQC (<em>D</em>-HMQC) scheme.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"122 ","pages":"Article 101835"},"PeriodicalIF":3.2,"publicationDate":"2022-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10337117","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}

{"title":"A case study on the influence of hydrophilicity on the signal enhancement by dynamic nuclear polarization","authors":"Sonja C. Döller ,&nbsp;Torsten Gutmann ,&nbsp;Markus Hoffmann ,&nbsp;Gerd Buntkowsky","doi":"10.1016/j.ssnmr.2022.101829","DOIUrl":"10.1016/j.ssnmr.2022.101829","url":null,"abstract":"<div><p><span>In this work, the behavior of four different commercially available polarizing agents is investigated employing the non-ionic model surfactant<span> 1-octanol as analyte. A relative method for the comparison of the proportion of the direct and indirect polarization transfer<span> pathways is established, allowing a direct comparison of the polarization efficacy for different radicals and different parts of the 1-octanol molecule despite differences in radical concentration or sample amount. With this approach, it could be demonstrated that the hydrophilicity is a key factor in the way polarization is transferred from the polarizing agent to the analyte. These findings are confirmed by the determination of buildup times T</span></span></span>_b<span>, illustrating that the choice of polarizing agent plays an essential role in ensuring an optimal polarization transfer and therefore the maximum amount of enhancement possible for DNP enhanced NMR measurements.</span></p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"122 ","pages":"Article 101829"},"PeriodicalIF":3.2,"publicationDate":"2022-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10397171","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}

{"title":"Solid-state NMR methods for the characterization of bioconjugations and protein-material interactions","authors":"Linda Cerofolini ,&nbsp;Giacomo Parigi ,&nbsp;Enrico Ravera ,&nbsp;Marco Fragai ,&nbsp;Claudio Luchinat","doi":"10.1016/j.ssnmr.2022.101828","DOIUrl":"10.1016/j.ssnmr.2022.101828","url":null,"abstract":"<div><p><span>Protein solid-state NMR has evolved dramatically over the last two decades, with the development of new hardware and sample preparation methodologies. This technique is now ripe for complex applications, among which one can count bioconjugation, protein </span>chemistry and functional biomaterials. In this review, we provide our account on this aspect of protein solid-state NMR.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"122 ","pages":"Article 101828"},"PeriodicalIF":3.2,"publicationDate":"2022-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"10341510","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}

{"title":"Narrowing down the conformational space with solid-state NMR in crystal structure prediction of linezolid cocrystals","authors":"Mehrnaz Khalaji,&nbsp;Piotr Paluch,&nbsp;Marek J. Potrzebowski,&nbsp;Marta K. Dudek","doi":"10.1016/j.ssnmr.2022.101813","DOIUrl":"10.1016/j.ssnmr.2022.101813","url":null,"abstract":"<div><p>Many solids crystallize as microcrystalline powders, thus precluding the application of single crystal X-Ray diffraction in structural elucidation. In such cases, a joint use of high-resolution solid-state NMR and crystal structure prediction (CSP) calculations can be successful. However, for molecules showing significant conformational freedom, the CSP-NMR protocol can meet serious obstacles, including ambiguities in NMR signal assignment and too wide conformational search space to be covered by computational methods in reasonable time. Here, we demonstrate a possible way of avoiding these obstacles and making as much use of the two methods as possible in difficult circumstances. In a simple case, our experiments led to crystal structure elucidation of a cocrystal of linezolid (LIN), a wide-range antibiotic, with 2,3-dihydroxybenzoic acid, while a significantly more challenging case of a cocrystal of LIN with 2,4-dihydroxybenzoic acid led to the identification of the most probable conformations of LIN inside the crystal. Having four rotatable bonds, some of which can assume many discreet values, LIN molecule poses a challenge in establishing its conformation in a solid phase. In our work, a set of 27 conformations were used in CSP calculations to yield model crystal structures to be examined against experimental solid-state NMR data, leading to a reliable identification of the most probable molecular arrangements.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"121 ","pages":"Article 101813"},"PeriodicalIF":3.2,"publicationDate":"2022-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S092620402200042X/pdfft?md5=a5776a2ee30ff0ec8d7bfcff5950a35e&pid=1-s2.0-S092620402200042X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40611293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solid-state NMR studies of metal ion and solvent influences upon the flexible metal-organic framework DUT-8","authors":"Marcus Rauche ,&nbsp;Sebastian Ehrling ,&nbsp;Leila Abylgazina ,&nbsp;Christopher Bachetzky ,&nbsp;Irena Senkovska ,&nbsp;Stefan Kaskel ,&nbsp;Eike Brunner","doi":"10.1016/j.ssnmr.2022.101809","DOIUrl":"10.1016/j.ssnmr.2022.101809","url":null,"abstract":"<div><p><span>Within the present contribution, we describe solid-state NMR spectroscopic studies of the paddle wheel unit in the prototypic flexible MOF compound DUT-8(M) (M = Ni, Co, Zn). The </span>¹³<span>C NMR chemical shift of these carboxylates shows a remarkable behavior. The pure 2,6-H</span>₂ndc linker carboxylates as well as DUT-8(Zn) exhibit a¹³C chemical shift of only about 170 ppm. In contrast, much higher values are observed for DUT-8(Ni) and especially DUT-8(Co). In the open pore state, the shift strongly depends on the solvent polarity in these two latter cases. The present contribution elucidates the reason for this solvent influence. It is concluded that the solvent mainly modifies the isotropic Fermi contact coupling constant for the excited high-spin states in DUT-8(Ni) and DUT-8(Co).</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101809"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40399789","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}

{"title":"Combining heteronuclear correlation NMR with spin-diffusion to detect relayed Cl–H–H and N–H–H proximities in molecular solids","authors":"Parth Raval ,&nbsp;Julien Trébosc ,&nbsp;Tomasz Pawlak ,&nbsp;Yusuke Nishiyama ,&nbsp;Steven P. Brown ,&nbsp;G.N. Manjunatha Reddy","doi":"10.1016/j.ssnmr.2022.101808","DOIUrl":"10.1016/j.ssnmr.2022.101808","url":null,"abstract":"<div><p>Analysis of short-to-intermediate range intermolecular interactions offers a great way of characterizing the solid-state organization of small molecules and materials. This can be achieved by two-dimensional (2D) homo- and heteronuclear correlation NMR spectroscopy, for example, by carrying out experiments at high magnetic fields in conjunction with fast magic-angle spinning (MAS) techniques. But, detecting 2D peaks for heteronuclear dipolar coupled spin pairs separated by greater than 3 Å is not always straightforward, particularly when low-gamma quadrupolar nuclei are involved. Here, we present a 2D correlation NMR experiment that combines the advantages of heteronuclear-multiple quantum coherence (HMQC) and proton-based spin-diffusion (SD) pulse sequences using radio-frequency-driven-recouping (RFDR) to probe inter and intramolecular ¹H-X (X = ¹⁴N, ³⁵Cl) interactions. This experiment can be used to acquire 2D ¹H{X}-HMQC filtered ¹H–¹H correlation as well as 2D ¹H-X HMQC spectra. Powder forms of dopamine·HCl and <span>l</span>-histidine·HCl·H₂O are characterized at high fields (21.1 T and 18.8 T) with fast MAS (60 kHz) using the 2D HMQC-SD-RFDR approach. Solid-state NMR results are complemented with NMR crystallography analyses using the gauge-including projector augmented wave (GIPAW) approach. For histidine·HCl·H₂O, 2D peaks associated with ¹⁴N–¹H–¹H and ³⁵Cl–¹H–¹H distances of up to 4.4 and 3.9 Å have been detected. This is further corroborated by the observation of 2D peaks corresponding to ¹⁴N–¹H–¹H and ³⁵Cl–¹H–¹H distances of up to 4.2 and 3.7 Å in dopamine·HCl, indicating the suitability of the HMQC-SD-RFDR experiments for detecting medium-range proximities in molecular solids.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101808"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926204022000376/pdfft?md5=060bbed25bd8792da9bf6f8e36de193b&pid=1-s2.0-S0926204022000376-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40555369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"19F Solid-state NMR characterization of pharmaceutical solids","authors":"Yong Du ,&nbsp;Yongchao Su","doi":"10.1016/j.ssnmr.2022.101796","DOIUrl":"10.1016/j.ssnmr.2022.101796","url":null,"abstract":"<div><p><span>Solid-state NMR has been increasingly recognized as a high-resolution and versatile spectroscopic tool to characterize drug substances and products. However, the analysis of pharmaceutical materials is often carried out at natural isotopic abundance and a relatively low drug loading in multi-component systems and therefore suffers from challenges of low sensitivity. The fact that fluorinated therapeutics are well represented in pipeline drugs and commercial products offers an excellent opportunity to utilize fluorine as a molecular probe for pharmaceutical analysis. We aim to review recent advancements of </span>¹⁹<span>F magic angle spinning NMR methods in modern drug research and development. Applications to polymorph screening at the micromolar level, structural elucidation, and investigation of molecular interactions at the Ångström to submicron resolution in drug delivery, stability, and quality will be discussed.</span></p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101796"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44659009","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}

{"title":"t1-noise elimination by continuous chemical shift anisotropy refocusing","authors":"Frédéric A. Perras ,&nbsp;Tian Wei Goh ,&nbsp;Wenyu Huang","doi":"10.1016/j.ssnmr.2022.101807","DOIUrl":"10.1016/j.ssnmr.2022.101807","url":null,"abstract":"<div><p><span>Due to their high gyromagnetic ratio, there is considerable interest in measuring distances and correlations involving protons, but such measurements are compounded by the simultaneous recoupling of chemical shift anisotropy (CSA). This secondary recoupling adds additional modulations to the signal intensities that ultimately lead to </span><em>t</em>₁-noise and signal decay. Recently, Venkatesh et al. demonstrated that the addition of CSA refocusing periods during ¹<span>H-X dipolar recoupling led to sequences with far higher stability and performance. Herein, we describe a related effort and develop a symmetry-based recoupling sequence that continually refocuses the </span>¹H CSA. This sequence shows superior performance to the regular and <em>t</em>₁<span>-noise eliminated D-HMQC sequences in the case of spin-1/2 nuclei and comparable performance to the later for half-integer quadrupoles.</span></p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101807"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49572288","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}

{"title":"High resolution solid state NMR in paramagnetic metal-organic frameworks","authors":"C.A. Klug ,&nbsp;M.W. Swift ,&nbsp;J.B. Miller ,&nbsp;J.L. Lyons ,&nbsp;A. Albert ,&nbsp;M. Laskoski ,&nbsp;C.M. Hangarter","doi":"10.1016/j.ssnmr.2022.101811","DOIUrl":"10.1016/j.ssnmr.2022.101811","url":null,"abstract":"<div><p>We study the metal-organic framework (MOF) ZIF-67 with ¹H and ¹³C nuclear magnetic resonance (NMR). In addition to the usual orbital chemical shifts, we observe spinning sideband manifolds in the NMR spectrum due to hyperfine interactions of the paramagnetic cobalt with ¹H and ¹³C. Both orbital and paramagnetic chemical shifts are in good agreement with values calculated from first principles, allowing high-confidence assignment of the observed peaks to specific sites within the MOF. Our measured resonance shifts, line shapes, and spin lattice relaxation rates are also consistent with calculated values. We show that molecules in the pores of the MOF can exhibit high-resolution NMR spectra with fast spin lattice relaxation rates due to dipole-dipole couplings to the Co²⁺ nodes in the ZIF-67 lattice, showcasing NMR spectroscopy as a powerful tool for identification and characterization of “guests” that may be hosted by the MOF in electrochemical and catalytic applications.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101811"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926204022000406/pdfft?md5=c4eb532d7f6257a0c6aa6ce21befe8f8&pid=1-s2.0-S0926204022000406-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40484908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing adsorption of water and DMF in UiO-66(Zr) using solid-state NMR","authors":"Florian Venel,&nbsp;Christophe Volkringer,&nbsp;Olivier Lafon,&nbsp;Frédérique Pourpoint","doi":"10.1016/j.ssnmr.2022.101797","DOIUrl":"10.1016/j.ssnmr.2022.101797","url":null,"abstract":"","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":"120 ","pages":"Article 101797"},"PeriodicalIF":3.2,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40395949","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}