A combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds.

We report solid-state 1H, 13C, and 17O NMR determination of hyperfine coupling tensors (A-tensors) in several paramagnetic Cu(II) (d9, S = 1/2) complexes: trans-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 A-tensor data available in the literature for trans-Cu(L-Ala)2 and K2CuCl4·2H2O, we were able to examine the accuracy of A-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated A-tensors on 1H (I = 1/2), 13C (I = 1/2), 14N (I = 1), 17O (I = 5/2), 39K (I = 3/2), 35Cl (I = 3/2), and 63Cu (I = 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 A-tensors and nuclear quadrupole coupling tensors.

1H/17O Chemical Shift Waves in Carboxyl-Bridged Hydrogen Bond Networks in Organic Solids.

We report solid-state 1H and 17O NMR results for four 17O-labeled organic compounds each containing an extensive carboxyl-bridged hydrogen bond (CBHB) network in the crystal lattice: tetrabutylammonium hydrogen di-[17O2]salicylate (1), [17O4]quinolinic acid (2), [17O4]dinicotinic acid (3), and [17O2]Gly/[17O2]Gly·HCl cocrystal (4). The 1H isotropic chemical shifts found for protons involved in different CBHB networks are between 8.2 and 20.5 ppm, which reflect very different hydrogen-bonding environments. Similarly, the 17O isotropic chemical shifts found for the carboxylate oxygen atoms in CBHB networks, spanning a large range between 166 and 341 ppm, are also remarkably sensitive to the hydrogen-bonding environments. We introduced a simple graphical representation in which 1H and 17O chemical shifts are displayed along the H and O atomic chains that form the CBHB network. In such a depiction, because wavy patterns are often observed, we refer to these wavy patterns as 1H/17O chemical shift waves. Typical patterns of 1H/17O chemical shift waves in CBHB networks are discussed. The reported 1H and 17O NMR parameters for the CBHB network models examined in this study can serve as benchmarks to aid in spectral interpretation for CBHB networks in proteins.

Effects of acute exposure to amisulbrom on retinal development in zebrafish (Danio rerio) embryos.

Amisulbrom is an oomycete-specific fungicide that was developed by Nissan Chemical Industries Limited. The exposure of developing zebrafish embryo to amisulbrom caused disorders in the visual phototransduction system. However, the potential toxic mechanisms of amisulbrom on retinal development remains unclear. The research purpose of this study was to evaluate the adverse effects of amisulbrom on retinal development in a model organism, the zebrafish. Zebrafish embryos were treated with 0, 0.0075, 0.075, or 0.75 µM amisulbrom from 3 h post-fertilization (hpf) to 72 hpf. Compared with the control group, amisulbrom-treated zebrafish embryos displayed phenotypic microphthalmia, dysregulation of gene transcription levels (alcama, prox1a, sox2, vsx1, rho, bluops, rdops, uvops, and grops) related to the retinal cell layer differentiation, and increased retinal apoptosis. In addition, the content of glutathione and malondialdehyde increased significantly after exposure to amisulbrom. Overall, our data demonstrate the toxicity of amisulbrom to eye development, which will help to assess the potential ecotoxicological impacts posed by amisulbrom to aquatic species.

31P NMR Chemical Shift Tensors: Windows into Ruthenium Phosphinidene Complex Electronic Structures.

A series of octamethylcalix[4]pyrrole/ruthenium phosphinidene complexes (Na2[1=PR]) can be accessed by phosphinidene transfer from the corresponding RPA (A = C14H10, anthracene) compounds (R = tBu, iPr, OEt, NH2, NMe2, NEt2, NiPr2, NA, dimethylpiperidino). Isolation of the tert-butyl and dimethylamino derivatives allowed comparative studies of their 31P nuclear shielding tensors by magic-angle-spinning solid-state nuclear magnetic resonance spectroscopy. Density functional theory and natural chemical shielding analyses reveal the relationship between the 31P chemical shift tensor and the local ruthenium/phosphorus electronic structure. The general trend observed in the 31P isotropic chemical shifts for the ruthenium phosphinidene complexes was controlled by the degree of deshielding in the δ11 principal tensor component, which can be linked to the σRuP/πRuP* energy gap. A "δ22-δ33 crossover" effect for R = tBu was also observed, which was caused by different degrees of deshielding associated with polarizations of the σPR and σPR* natural bond orbitals.

Solid-State 17O NMR Studies of Sulfonate Jump Dynamics in Crystalline Sulfonic Acids: Insights into the Hydrogen Bonding Effect.

We report variable-temperature (VT) 17O solid-state nuclear magnetic resonance (NMR) spectra for three crystalline sulfonic acids: l-cysteic acid monohydrate (CA), 3-pyridinesulfonic acid (PSA), and p-toluenesulfonic acid monohydrate (TSA). We were able to analyze the experimental VT 17O NMR spectra to obtain the activation barriers for SO3- jumps in these systems. Using the density functional-based tight-binding (DFTB) method, we performed potential energy surface scans for SO3- jumps in the crystal lattice of CA, PSA, and TSA, as well as for three related crystalline sulfonic acids (taurine, homotaurine, and 4-aminobutane-1-sulfonic acid) for which relevant 17O solid-state NMR data are available in the literature. The calculated activation barriers are in reasonable agreement with the experimental values. On the basis of the DFTB results, we hypothesized that activation barriers for SO3- jumps in the crystal lattice depend largely on the hydrogen bonding energy difference between the ground state and the transition state.

Solid-State 15N and 17O NMR Studies of S-Nitrosothiols.

We report a solid-state 15N and 17O NMR study of two representative S-nitrosothiols (RSNO): S-nitroso N-acetylpenicillamine (SNAP) and S-nitrosoglutathione (GSNO). The 15N and 17O NMR tensors are experimentally determined for the first time for this important class of nitric-oxide (NO)-related compounds. The observed NMR characteristics for RSNO include large 15N and 17O chemical shift anisotropies and large 17O quadrupole coupling constants. Quantum chemical calculations are also performed for the 15N and 17O NMR tensors in two simple RSNO models: t-BuSNO and MeSNO. On the basis of computational results, we have identified the molecular orbitals that are responsible for the observed large chemical shift anisotropies in RSNO compounds.

Solid-state 17O NMR study of 2-acylbenzoic acids and warfarin.

We report synthesis and solid-state 17O NMR characterization of four site-specifically 17O-labeled 2-acylbenzoic acids (2-RC(O)C6H4COOH) where R=H and CH3): 2-[3-17O]formylbenzoic acid, 2-[1,2-17O2]formylbenzoic acid, 2-[3-17O]acetylbenzoic acid, and 2-[1,2,3-17O3]acetylbenzoic acid. In the solid state, both 2-formyl- and 2-acetyl-benzoic acids exist as the cyclic phthalide form each containing a five-membered lactone ring and a cyclic hemiacetal/hemiketal group. Static and magic-angle-spinning 17O NMR spectra were recorded at 14.1 and 21.1T for these compounds, from which the 17O chemical shift and nuclear quadrupolar coupling tensors were determined for each oxygen site. These results represent the first time that 17O NMR tensors are fully characterized for lactone, cyclic hemiacetal, and cyclic hemiketal functional groups. We also report solid-state 17O NMR data for the cyclic hemiketal group an anticoagulant drug, warfarin. Experimental 17O NMR tensors in these compounds were compared with computational results obtained with a periodic DFT code BAND.

Multi-electron reactivity of a cofacial di-tin(ii) cryptand: partial reduction of sulfur and selenium and reversible generation of S3˙.

Cofacial bimetallic tin(ii) ([Sn2(mBDCA-5t)]2-, 1) and lead(ii) ([Pb2(mBDCA-5t)]2-, 2) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand mBDCA-5t-H6 together with double Sn(ii) or Pb(ii) insertion. Reaction of 1 with elemental sulfur or selenium generates di-tin polychalcogenide complexes containing µ-E and bridging µ-E5 ligands where E = S or Se, and the Sn(ii) centers have both been oxidized to Sn(iv). Solution and solid-state UV-Vis spectra of [(µ-S5)Sn2(µ-S)(mBDCA-5t)]2- (4) indicate that the complex acts reversibly as a source of S3˙- in DMF solution with a Keq = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(µ-E5)Sn2(µ-E)(mBDCA-5t)]2- with PR3 (R = t Bu, Ph, OiPr) to produce six equiv. of the corresponding EPR3 compound with regeneration of di-tin(ii) cryptand complex 1.