Interplay Between π‑Stacking and Hydrogen Bonding in the Self-Association of Different Isomers of Naphthalenedicarboxylic Acid

Using proton and carbon chemical shifts, we investigated the self-association of three isomers of naphthalenedicarboxylic acid, a model for the aggregation of asphaltenes. Experimental proton chemical shifts of each isomer were measured as a function of concentration in an aprotic solvent. Several potential structures of the monomer and dimer of each naphthalenedicarboxylic acid were considered, and calculated proton chemical shifts for the potential monomer and dimer structures were compared to the experimental chemical shifts to find the weighted average structure that best fit the experimental shifts. Calculated carbon chemical shifts were also compared to experimental values. The chemical shift comparison and calculated energies indicate that π-stacked dimers are not likely to contribute significantly to the dimer structure of any of the three naphthalenedicarboxylic acid isomers studied

Examining Binding to Nanoparticle Surfaces Using Saturation Transfer Difference (STD)-NMR Spectroscopy

The interaction of molecules with the surface of nanoparticles is important in many fields of study, including drug delivery and nanoparticle toxicity. Solution-state NMR has the potential to provide structural as well as dynamic information regarding molecules adsorbed to the nanoparticle surface. Here, we use Saturation-Transfer Difference NMR (STD-NMR) to examine small molecules binding to the surface of polystyrene nanoparticles. Binding constants for this nonspecific adsorption are determined from the initial slope of the STD buildup curve at several ligand concentrations. We also use the STD-NMR technique to quantify the association of solvent water molecules with the nanoparticle surface. The results presented here will be useful to future studies involving peptides and proteins adsorbed on nanoparticle surfaces

NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional ¹³C Solid-State NMR and ab Initio Chemical Shift Calculations

Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D ¹³C double-quantum/single-quantum correlation SSNMR spectrum of ¹³C-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf−Klinowski model (Lerf, A. et al. <i>Phys. Chem. B</i> <b>1998</b>, <i>102</i>, 4477); this model is composed of interconnected sp², 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. <i>Chem. Mater.</i> <b>2006</b>, <i>18</i>, 2740). ¹³C chemical shift anisotropy (CSA) patterns measured by a 2D ¹³C CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems

Progress in 13C and 1H solid-state nuclear magnetic resonance for paramagnetic systems under very fast magic angle spinning.

High-resolution solid-state NMR (SSNMR) of paramagnetic systems has been largely unexplored because of various technical difficulties due to large hyperfine shifts, which have limited the success of previous studies through depressed sensitivity/resolution and lack of suitable assignment methods. Our group recently introduced an approach using "very fast" magic angle spinning (VFMAS) for SSNMR of paramagnetic systems, which opened an avenue toward routine analyses of small paramagnetic systems by (13)C and (1)H SSNMR [Y. Ishii et al., J. Am. Chem. Soc. 125, 3438 (2003); N. P. Wickramasinghe et al., ibid. 127, 5796 (2005)]. In this review, we discuss our recent progress in establishing this approach, which offers solutions to a series of problems associated with large hyperfine shifts. First, we demonstrate that MAS at a spinning speed of 20 kHz or higher greatly improves sensitivity and resolution in both (1)H and (13)C SSNMR for paramagnetic systems such as Cu(II)(DL-alanine)(2)H(2)O (Cu(DL-Ala)(2)) and Mn(acac)(3), for which the spectral dispersions due to (1)H hyperfine shifts reach 200 and 700 ppm, respectively. Then, we introduce polarization transfer methods from (1)H spins to (13)C spins with high-power cross polarization and dipolar insensitive nuclei enhanced by polarization transfer (INEPT) in order to attain further sensitivity enhancement and to correlate (1)H and (13)C spins in two-dimensional (2D) SSNMR for the paramagnetic systems. Comparison of (13)C VFMAS SSNMR spectra with (13)C solution NMR spectra revealed superior sensitivity in SSNMR for Cu(DL-Ala)(2), Cu(Gly)(2), and V(acac)(3). We discuss signal assignment methods using one-dimensional (1D) (13)C SSNMR (13)C-(1)H rotational echo double resonance (REDOR) and dipolar INEPT methods and 2D (13)C(1)H correlation SSNMR under VFMAS, which yield reliable assignments of (1)H and (13)C resonances for Cu(Ala-Thr). Based on the excellent sensitivity/resolution and signal assignments attained in the VFMAS approach, we discuss methods of elucidating multiple distance constraints in unlabeled paramagnetic systems by combing simple measurements of (13)C T(1) values and anisotropic hyperfine shifts. Comparison of experimental (13)C hyperfine shifts and ab initio calculated shifts for alpha- and beta-forms of Cu(8-quinolinol)(2) demonstrates that (13)C hyperfine shifts are parameters exceptionally sensitive to small structural difference between the two polymorphs. Finally, we discuss sensitivity enhancement with paramagnetic ion doping in (13)C SSNMR of nonparamagnetic proteins in microcrystals. Fast recycling with exceptionally short recycle delays matched to short (1)H T(1) of approximately 60 ms in the presence of Cu(II) doping accelerated 1D (13)C SSNMR for ubiquitin and lysozyme by a factor of 7.3-8.4 under fast MAS at a spinning speed of 40 kHz. It is likely that the VFMAS approach and use of paramagnetic interactions are applicable to a variety of paramagnetic systems and nonparamagnetic biomolecules