Solid state nuclear magnetic resonance最新文献

{"title":"Theoretical investigation of the effects of diverse hydrogen-bonding characteristics on the 17O chemical shielding and electric field gradient tensors within the active sites of MraYAA bound to nucleoside antibiotics capuramycin, carbacaprazamycin, 3′-Hydroxymureidomycin A, and muraymycin D2","authors":"","doi":"10.1016/j.ssnmr.2024.101960","DOIUrl":"10.1016/j.ssnmr.2024.101960","url":null,"abstract":"<div><p>This study builds upon our prior researches and seeks to investigate and clarify the influences of various characteristics of hydrogen bonds (H-bonds) and charge transfer (CT) interactions, which were detected within the inhibitor binding pockets (labeled as the QM models I–IV) of MraY_AA–capuramycin, MraY_AA–carbacaprazamycin, MraY_AA–3′-hydroxymureidomycin A, and MraY_AA–muraymycin D2 complexes by QTAIM and NBO analyses from DFT QM/MM MD calculations, on the ¹⁷O chemical shielding (CS) and electric field gradient (EFG) tensors of carboxylate (Oδ), carbonyl (C═O), and hydroxyl (O–H) oxygens in these models. The ¹⁷O CS and EFG tensors of these three types of oxygens in QM models I–IV were calculated at the M06-2X/6-31G** level by including the solvent effects using the polarizable continuum model. From the computed ¹⁷O CS and EFG tensors in these models, it was found that the nuclear shielding, σ_iso, for carboxylate or carbonyl oxygen increases (shielding effect) as the H-bond length decreases and the percentage p-character of <em>n</em>_Oδ/<em>n</em>_C═O lone pair partner in the CT interaction enhances. In contrast, the σ_iso (¹⁷O–H) decreases (deshielding effect) with a reduction in the H-bond length as well as with an enhancement in percentage s-character of the <em>n</em>_OH lone pair/σ*_O–H antibond. By reducing the H-bond length or by increasing p-character of the <em>n</em>_Oδ/<em>n</em>_C═O lone pair, the ¹⁷Oδ/¹⁷O═C quadrupole coupling constant smoothly decreases, while the ¹⁷Oδ/¹⁷O═C asymmetry parameter smoothly increases. Moreover, these calculated parameters are in a good agreement with the experimental values. The information garnered here is valuable particularly for further understanding of empirical correlations between ¹⁷O NMR spectroscopic and H-bonding characteristics in the protein–ligand complexes.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142087875","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":"Cooperative β-sheet coassembly controls intermolecular orientation of amphiphilic peptide-polydiacetylene conjugates","authors":"","doi":"10.1016/j.ssnmr.2024.101959","DOIUrl":"10.1016/j.ssnmr.2024.101959","url":null,"abstract":"<div><p>In this work, we elucidated the structural organization of stimuli-responsive peptide-polydiacetylene (PDA) conjugates that can self-assemble as 1D nanostructures under neutral aqueous conditions. The amino acid sequences bear positively or negatively charged domains at the periphery of the peptide segments to promote solubility in water while also driving assembly of the individual and combined components into β-sheets. The photopolymerization of PDA, as well as the sensitivity of the resulting optical properties of the polymeric material to external stimuli, highly depends on the structural organization of the assembly of amphiphilic peptide-diacetylene units into 1D-nanostructures. Solid-state NMR measurements on ¹³C-labeled and ¹⁵N-labeled samples show that positively charged and negatively charged peptide amphiphiles are each capable of self-assembly, but self-assembly favors antiparallel β-sheet structure. When positively and negatively charged peptide amphiphiles interact in stoichiometric solutions, cooperative coassembly dominates over self-assembly, resulting in the desired parallel β-sheet structure with a concomitant increase in structural order. These results reveal that rational placement of oppositely charged residues can control β-strand organization in a peptide amphiphile coassembly, which would have implications on the adaptive properties of stimuli-responsive biomaterials such as the peptide-PDAs studied here.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142096517","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":"Predicting 35-Cl electric field gradient tensors in crystalline solids using cluster and fragment-corrected planewave density functional theory","authors":"","doi":"10.1016/j.ssnmr.2024.101949","DOIUrl":"10.1016/j.ssnmr.2024.101949","url":null,"abstract":"<div><p>Planewave-corrected methods have proven effective for accurately modeling nuclear magnetic resonance (NMR) parameters in crystalline systems. Recent work extended the application of planewave-corrected calculations beyond the second row, predicting EFG tensor parameters for ³⁵Cl using a simple molecular correction to projector augmented-wave (PAW) density functional theory (DFT). Here we extend this work using fragment and cluster-based calculations coupled with polarizable continuum (PCM) methods to improve further the accuracy of planewave-corrected ³⁵Cl EFG tensor calculations. Benchmark data from a test set comprised of 105 individual ³⁵Cl EFG tensor principal components for chlorine-containing molecular crystals and crystalline chloride salts shows fragment-corrected planewave calculations using the PBE0 hybrid density functional improve the accuracy of predicted EFG tensor components by 30 % relative to traditional planewave calculations. We compare the influence of different geometry optimization methods and density functionals on the accuracy of predicted ³⁵Cl EFG tensor parameters. Four cases of spectral assignment are presented to demonstrate the utility of improving the accuracy of predicted ³⁵Cl EFG tensor parameters.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142049260","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":"Phenolic syringyl end groups in 13C-enriched hardwoods detected and quantified by solid-state NMR","authors":"","doi":"10.1016/j.ssnmr.2024.101947","DOIUrl":"10.1016/j.ssnmr.2024.101947","url":null,"abstract":"<div><p>While syringyl units are the most abundant monolignols in hardwood lignin, their phenolic (i.e. hydroxyl) end group concentration has not been measured. In two uniformly ¹³C-enriched young hardwoods, from beech and oak, the syringyl units were quantitatively investigated by advanced solid-state ¹³C NMR. Small signals of OH-terminated syringyl units were resolved in spectrally edited two-dimensional ¹³C–¹³C NMR spectra of the two hardwoods. Their distinct peak positions predicted based on literature data were validated via the abundant OH-terminated syringyl units in hydrolyzed ¹³C-beechwood. In a two-dimensional ¹³C–¹³C exchange spectrum with diagonal-ridge suppression, a well-resolved peak of phenolic syringyl units was observed at the characteristic C–H peak position of syringyl rings, without significant overlap from guaiacyl peaks. Accurate ¹³C chemical shifts of regular and end-group syringyl units were obtained. Through spectrally edited 2D NMR after ¹H inversion recovery, phenols of condensed tannin complexed with arginine were carefully analyzed and shown to overlap minimally with signals from phenolic syringyl units. The local structure and resulting spin dynamics of ether (chain) and hydroxyl (end-group) syringyl units are nearly the same, enabling quantification by peak integration or deconvolution, which shows that phenolic syringyl end groups account for 2 ± 1 % of syringyl units in beechwood and 5 ± 2 % in oakwood. The observed low end-group concentration needs to be taken into account in realistic molecular models of hardwood lignin structure.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141789075","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":"Ultra wideline dipolar NMR spectroscopy: Combining SEDOR and WURST-CPMG","authors":"Ulrich Rehfuß, Josef Maximilian Gerdes, Renato Grigolon Capelo, Danilo Manzani, Michael Ryan Hansen, Hellmut Eckert, L. van Wüllen","doi":"10.1016/j.ssnmr.2024.101948","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2024.101948","url":null,"abstract":"","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141848863","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 Numerical simulation method for analyzing 1H spin diffusion NMR for Multicomponent and multiphase polymer systems","authors":"Xuran Jin ,&nbsp;Wei Chen","doi":"10.1016/j.ssnmr.2024.101946","DOIUrl":"10.1016/j.ssnmr.2024.101946","url":null,"abstract":"<div><p>A numerical simulation method, namely, <em>SDNMR-WEBFIT</em>, is reported for simulating proton spin diffusion NMR based on the Levenberg-Marquardt algorithm and a pseudo-2D diffusion model. This method is used for the precise quantification of dynamics heterogeneity of the interphase within multiphase polymer systems. The numerical simulation method provides measurements of spin-lattice relaxation time (<em>T</em>₁), proton density (<em>ρ</em>_H), lamellar thickness (<em>d</em>), and spin diffusion coefficient (<em>D</em>) for each component. The pseudo-2D diffusion model is employed to simulate the proton spin diffusion build-up/decay curves, simultaneously calculating the lateral fraction of island-like structures (<em>x</em>-ratio). Such approach was successfully applied to various polymer systems, such as semi-crystalline polymer (Poly(ε-caprolactone), PCL), block copolymers (Styrene-butadiene-styrene triblock copolymer, SBS), and plasticized semi-polymers (Polvinyl alcohol, PVA).</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463757","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 combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds","authors":"Yizhe Dai ,&nbsp;Victor Terskikh ,&nbsp;Gang Wu","doi":"10.1016/j.ssnmr.2024.101945","DOIUrl":"10.1016/j.ssnmr.2024.101945","url":null,"abstract":"<div><p>We report solid-state ¹H, ¹³C, and ¹⁷O NMR determination of hyperfine coupling tensors (<em>A</em>-tensors) in several paramagnetic Cu(II) (<em>d</em>⁹, <em>S</em> = 1/2) complexes: <em>trans</em>-Cu(DL-Ala)₂·H₂¹⁷O, Cu([1–¹³C]acetate)₂·H₂O, Cu([2–¹³C]acetate)₂·H₂O, and Cu(acetate)₂·H₂¹⁷O. Using these new experimental results and some <em>A</em>-tensor data available in the literature for <em>trans</em>-Cu(L-Ala)₂ and K₂CuCl₄·2H₂O, we were able to examine the accuracy of <em>A</em>-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated <em>A</em>-tensors on ¹H (<em>I</em> = 1/2), ¹³C (<em>I</em> = 1/2), ¹⁴N (<em>I</em> = 1), ¹⁷O (<em>I</em> = 5/2), ³⁹K (<em>I</em> = 3/2), ³⁵Cl (<em>I</em> = 3/2), and ⁶^³Cu (<em>I</em> = 3/2) nuclei over a range spanning more than 3 orders of magnitude. We found that the BAND code can reproduce reasonably well the experimental results for both <em>A</em>-tensors and nuclear quadrupole coupling tensors.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926204024000316/pdfft?md5=ae64e66e28bb0afa12d18d1f523805f6&pid=1-s2.0-S0926204024000316-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141538619","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":"Anisotropic relaxation of nuclear spins dipolar energy of water molecules in two-dimensional nanopores - A single crystal NMR study","authors":"Alexander M. Panich ,&nbsp;Jan Swenson","doi":"10.1016/j.ssnmr.2024.101944","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2024.101944","url":null,"abstract":"<div><p>Energy transfer from Zeeman to dipolar order discovered by Jeener et al. is usually observed in solids with a strong dipole-dipole interaction of nuclear spins. It is not observed in liquids, where fast molecular motion completely averages this interaction. The intermediate case, when the dipole-dipole interaction of nuclear spins is only partially averaged, has been poorly studied. We report on the first measurement of an angular-dependent proton spin relaxation of a dipolar reservoir in mobile water molecules confined in the interlayer pores of a vermiculite single crystal. In this layered crystal, the intramolecular dipole-dipole interactions of nuclear spins are only partially averaged due to the restricted anisotropic molecular motion in nanopores. We show that this allows the formation of dipolar echo. We measured the spin-lattice relaxation times of the dipolar order <em>T</em>_<em>1D</em> at different angles between the normal to the crystal surface and the applied magnetic field and obtained a distinct angular dependence of <em>T</em>_<em>1D</em>. The minimum relaxation rate <em>R</em>_<em>1D</em> was found around the magic angle of 54.74°.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141438408","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":"Microscopic understanding of NMR signals by dynamic mean-field theory for spins","authors":"Timo Gräßer ,&nbsp;Thomas Hahn ,&nbsp;Götz S. Uhrig","doi":"10.1016/j.ssnmr.2024.101936","DOIUrl":"10.1016/j.ssnmr.2024.101936","url":null,"abstract":"<div><p>A recently developed dynamic mean-field theory for disordered spins (spinDMFT) is shown to capture the spin dynamics of nuclear spins very well. The key quantities are the spin autocorrelations. In order to compute the free induction decay (FID), pair correlations are needed in addition. They can be computed on spin clusters of moderate size which are coupled to the dynamic mean fields determined in a first step by spinDMFT. We dub this versatile approach non-local spinDMFT (nl-spinDMFT). It is a particular asset of nl-spinDMFT that one knows from where the contributions to the FID stem. We illustrate the strengths of nl-spinDMFT in comparison to experimental data for CaF₂. Furthermore, spinDMFT provides the dynamic mean fields explaining the FID of the nuclear spins of ¹³C in adamantane up to some static noise. The spin Hahn echo in adamantane is free from effects of static noise and agrees excellently with the spinDMFT results without further fitting.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926204024000225/pdfft?md5=5c5e65aad81fd60774cb14a23ee84b0f&pid=1-s2.0-S0926204024000225-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141182730","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":"Automatic fitting of multiple-field solid-state NMR spectra","authors":"Frédéric A. Perras ,&nbsp;Alexander L. Paterson","doi":"10.1016/j.ssnmr.2024.101935","DOIUrl":"https://doi.org/10.1016/j.ssnmr.2024.101935","url":null,"abstract":"<div><p>The NMR lineshapes produced by half-integer quadrupolar nuclei are sensitive to 11 distinct fit parameters per inequivalent site. To date, automatic fitting routines have failed to replace manual parameter insertion and evaluation due to the importance of local minima and the need for fitting multiple-field magic-angle spinning (MAS) and static spectra simultaneously. Herein we introduce a new tool, AMES-Fit (Automatic Multiple Experiment Simulation and Fitting), to automatically find the global best-fit simulation parameters for a series of multiple-field NMR lineshapes. AMES-Fit uses an adaptive step size random search algorithm to dynamically probe parameter space and requires minimal human input. The best fits are obtained in a few minutes of computation time that would otherwise have required several person-hours of work. The program is freely available and open-source.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140543926","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}