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Serial NMR experiments are commonly applied in variable-temperature studies, reaction monitoring, and other tasks. The resonance frequencies often shift linearly over the series, and the shift rates help to characterize the studied system. They can be determined using a classical fitting of peak positions or a more advanced method of Radon transform. However, the optimal procedure for data collection remains to be determined. In this paper, we discuss how to invest experimental time, i.e., whether to measure more scans at the expense of the number of spectra or vice versa. The results indicate that classical fitting provides slightly less error than the Radon transform, although the latter can be the method of choice for a low signal-to-noise ratio. We demonstrate this fact through theoretical consideration, simulations, and an experiment. Finally, we extend our considerations to the linear fitting of peak amplitudes. Interestingly, the optimal setup for measuring peak height changes differs from the one for resonance frequency changes - fewer spectra with more scans provide better results.

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Selective catalytic reduction (SCR) of NOx by ammonia is one of the dominant pollution abatement technologies for near-zero NOx emission diesel engines. A crucial step in the reduction of NOx to N2 with Cu zeolite NH3-SCR catalysts is the generation of a multi-electron donating active site, implying the permanent or transient dimerization of Cu ions. Cu atom mobility has been implicated by computational chemistry as a key factor in this process. This report demonstrates how variable temperature 1H NMR reveals the Cu induced generation of sharp 1H resonances associated with a low concentration of sites on the zeolite. The onset temperature of the appearance of these signals was found to strongly correlate with the NH3-SCR activity and was observed for a range of catalysts covering multiple frameworks (CHA, AEI, AFX, ERI, ERI-CHA, ERI-OFF, *BEA), with different Si/Al ratios and different Cu contents. The results point towards universal applicability of variable temperature NMR to predict the activity of a Cu-zeolite SCR catalyst. The unique relationship of a spectroscopic feature with catalytic behavior for zeolites with different structures and chemical compositions is exceptional in heterogeneous catalysis.

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Hinge motion is observed in macrocyclic, mortise-type molecular hinges using variable temperature NMR spectroscopy. The data is consistent with dynamic hinging from a folded-to-extended-to-folded enantiomeric state. Crystallographic and solution structures of the folded states are reported. Chemical shift predictions derived from crystallographic data corroborate fully revolute hinge motion. The rate of hinging is affected by steric congestion at the hinge axis. A macrocycle containing glycine, 1, hinges faster than one comprising aminoisobutyric acid, 2. The free energies of activation, ΔG≠ , for 1 and 2 were determined to be 13.3±0.3 kcal/mol and 16.3±0.3 kcal/mol, respectively. This barrier is largely independent of solvent across those surveyed (CD3 OD, CD3 CN, DMSO-d6 , pyridine-d5 , D2 O). Experiment and computation predict energy barriers that are consistent with disruption of an intramolecular network of hydrogen bonds. DFT calculations reveal a pathway for hinge motion.

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We now report that some chiral compounds, like alcohols, which are not sterically hindered atropisomers nor epimer mixtures, exhibit two sets of simultaneous NMR spectra in CDCl3. Some other chiral alcohols also simultaneously exhibit two different NMR spectra in the solid state because two different conformers, A and B had different sizes because their corresponding bond lengths and angles are different. These structures were confirmed in the same solid state by X-ray. We designate these as pseudo-resonance for a compound exhibiting several different corresponding lengths that simultaneously coexist in the solid state or liquid state. Variable-temperature NMR, 2D NMR methods, X-ray, neutron diffraction, IR, photo-luminesce (PL) and other methods were explored to study whether new aggregation states caused these heretofore unknown pseudo-resonance structures. Finally, eleven chiral alcohols or diols were found to co-exist in pseudo-resonance structures by X-ray crystallography in a search of the CDS database.

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The 13C signals of adamantane are used as a chemical shift standard for solid-state NMR. Its chemical shifts are measured to greater accuracy than previously reported and over a temperature range from -2 to 70 °C. Combining the chemical shifts of adamantane's two NMR signals gives an accurate chemical shift over the whole temperature range without need for measuring the temperature directly. The difference between the chemical shifts gives the approximate temperature. The chemical shift of the adamantane CH signal at 25 °C is 37.777, σ = 0.003 ppm.

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Low-temperature NMR studies with a 4-C-methyl-4-O-benzoyl galactopyranosyl donor enable the observation and characterization of a bridged bicyclic dioxacarbenium ion arising from participation by a distal ester. Variable-temperature NMR studies reveal this bridged ion to decompose at temperatures above ≈-30 °C. In the absence of the methyl group, the formation of a bicyclic ion is not observed. It is concluded that participation by typical secondary distal esters in glycosylation reactions is disfavored in the ground state conformation of the ester from which it is stereoelectronically impossible. Methylation converts the secondary ester to a conformationally more labile tertiary ester, removes this barrier, and renders participation more favorable. Nevertheless, the minor changes in selectivity in model glycosylation reactions on going from the secondary to the tertiary esters at both low and room temperature argue against distal group participation being a major stereodirecting factor even for the tertiary system.

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The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)3 were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)3 complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)3 were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)3. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d'); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol-1. Notably, PBE0/BS1 describes the (CO)3 rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)3 complexes (except for (TMCOT)W(CO)3), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)3 complex (computed with the PBE0 functional) has a ΔG‡ of 12.6, 12.8, and 13.2 kcal mol-1 for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed 1H-NMR and 13C-NMR chemical shifts for (TMCOT)Cr(CO)3 and (TMCOT)Mo(CO)3 at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures.

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Herein we report general methods allowing the synthesis of various perfluoroalkylated corannulenes with a specific substitution pattern. Variable temperature NMR spectroscopic investigations revealed dynamic behavior which was analyzed by line shape analysis. The activation parameters of these dynamic processes were determined. For a tetrasubstituted compound it was possible to observe through space scalar coupling. The packing motifs were elucidated by X-ray crystallography, showing that the substitution pattern as well as the size of substituents strongly influence intermolecular π-stacking. The reduction potentials of the perfluoroalkylated compounds were determined by cyclic voltammetry.

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A thermo-responsive cellulose-based material (cellulose-g-PNIPAAm) was prepared by grafting N-isopropylacrylamide (NIPAAm) onto bagasse pulp cellulose via Ce (IV)-initiated free radical polymerization. The surfaces of the obtained cellulose-g-PNIPAAm paper showed a rapid wettability conversion from being hydrophilic (water contact angles (WCA) of 0°) at 25 °C to becoming hydrophobic (WCA of 134.2°) at 45 °C. Furthermore, the thermo-responsive mechanism of cellulose-g-PNIPAAm was examined by the in situ variable-temperature 13C NMR, ¹H NMR and AFM analysis. At the same time, the resulting cellulose paper was applied for a switchable separation of oil/water mixtures. Water can pass through the paper under 45 °C, while oil is kept on the paper. When the temperature is above 45 °C, oil can permeate through the paper, while water cannot pass through the water. Moreover, the paper exhibited excellent regeneration performance after five cycles and maintained its switchable wettability.

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In this work, changes in microstructure of two protic ionic liquids (PILs), namely n-butylammonium acetate (N4Ac) and n-butylammonium nitrate (N4NO3 ), are proved by in situ variable-temperature 1 H NMR spectroscopy at the temperature range from 25 to 115 °C, and the influence of the nature of anion is discussed accordingly. The results demonstrate that 1 H NMR chemical shifts of alkyl protons of both N4Ac and N4NO3 are almost not changed with the increasing of temperature, due to the absence of hydrogen bond interaction between alkyl protons with anions. Whereas those of + N-H of cation decrease linearly with the temperature increasing, indicating that the hydrogen bond interaction between + N-H and anion weakens gradually. In addition, the strength of hydrogen bond interaction between + N-H and NO3- is stronger than that between + N-H and Ac- , suggesting that anions have a significant influence on microstructure due to the acidity of a Brønsted acid. Consequently, the proton transfer from cation to anion is much easier in N4Ac compared to N4NO3 . Further analyses of 1 H NMR chemical shifts of + N-H in N4Ac at the temperature range from 100 to 115 °C suggest that the splitting of + N-H peak may be attributed to obvious evidence of the existence of the proton transfer from + N-H to Ac- , which leads to dissociate the contact ion-pair in N4Ac to form the neutral ion-pair 'molecule'. The results will help us to extensively understand the behavior of proton transfer and offer us some valuable information for the design of PILs. Copyright © 2017 John Wiley & Sons, Ltd.

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We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)2-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

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Previous activity-guided phytochemical studies on Garcinia buchananii stem bark, which is traditionally used in Africa to treat various gastrointestinal and metabolic illnesses, revealed xanthones, polyisoprenylated benzophenones, flavanone-C-glycosides, biflavonoids, and/or biflavanones as bioactive key molecules. Unequivocal structure elucidation of biflavonoids and biflavanones by means of NMR spectroscopy is often complicated by the hindered rotation of the monomers around the C-C axis (atropisomerism), resulting in a high spectral complexity. In order to facilitate an unrestricted rotation, NMR spectra are usually recorded at elevated temperatures, commonly over 80 °C, which effects in a single set of resonance signals. However, under these conditions, one of the target compounds of this investigation, (2R,3S,2″R,3″R)-manniflavanone (1), undergoes degradation. Therefore, we demonstrated in the present study that the 1,1-ADEQUATE could be successfully used as a powerful alternative approach to confirm the C-C connectivities in 1, avoiding detrimental conditions. However, a moderate increase in temperature up to 50 °C was sufficient to deliver sharp signals in the proton NMR experiment of (2R,3S,2″R,3″R)-isomanniflavanone (2) and (2″R,3″R)-preussianone (3). In addition, two new compounds could be isolated, namely (2R,3S,2″R,3″R)-GB-2 7″-O-ß-D-glucopyranoside (4) and (2R,3S,2″R,3″R)-manniflavanone-7″-O-ß-D-glucopyranoside (5), and whose structures were elucidated by spectroscopic analysis including 1D and 2D NMR and mass spectrometry methods. The absolute configurations were determined by a combination of NMR and electronic circular dichroism (ECD) spectroscopy. The aforementioned compounds exhibited high anti-oxidative capacity in the H2O2 scavenging, hydrophilic Trolox equivalent antioxidant capacity (H-TEAC) and hydrophilic oxygen radical absorbance capacity (H-ORAC) assays.

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Planar (N-benzyl-N-furfuryldithiocarbamato-S,S')(thiocyanato-N)(triphenylphospine)nickel(II), [Ni(bfdtc)(NCS)(PPh3)], (1) was prepared from bis(N-benzyl-N-furfuryldithiocarbamato-S,S')nickel(II), [Ni(bfdtc)2], (2) and characterized by elemental analysis, cyclic voltammetry, electronic, IR and variable temperature (1)H and (13)C NMR spectra. For complex 1, the thioureide vCN value is shifted to higher wavenumber compared to 2 and N(13)CS2 carbon signal observed for 1 is additionally shielded compared to the parent complex 2, suggesting increased strength of the thioureide bond due to the presence of the π-accepting phosphine. In the room temperature (13)C NMR spectrum of 1, two pseudo doublets are observed in the aliphatic region. Variable temperature (13)C NMR spectral studies suggest that the fast thiocyanate exchange appears to be responsible for the appearance of pseudo doublets. Single crystal X-ray structural analysis of 1 and 2 confirm the presence of four coordinated nickel in a distorted square planar arrangement with the NiS2PN and NiS4 chromophores, respectively. The NiS bonds are symmetric in 2 (2.1914(14) and 2.2073(13)Å). But significant asymmetry in NiS bond distances was observed in 1 (2.2202(8)Å and 2.1841Å). This observation clearly supports the less effective trans effect of SCN(-) over PPh3. Cyclic voltammetric studies revealed easier reduction of nickel(II) to nickel(I) in complex 1 compared to 2.

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The genus Garcinia is reported to possess antimicrobial, anti-inflammatory, anticancer, hepatoprotective and anti-HIV activities. Garcinia hombroniana in Malaysia is used to treat itching and as a protective medicine after child birth. This study was aimed to isolate the chemical constituents from the bark of G. hombroniana and explore their possible pharmacological potential. Ethyl acetate extract afforded one new (1) and six (2-7) known 3 → 8 rotameric biflavonoids. Their structures were elucidated by UV, IR and NMR (1D and 2D) spectroscopy together with electron ionization/ESI mass spectrometric techniques and were identified as (2R, 3S) volkensiflavone-7-O-rhamnopyranoside (1), volkensiflavone (2), 4″-O-methyl-volkensiflavone (3), volkensiflavone-7-O-glucopyranoside (4), morelloflavone (5), 3″-O-methyl-morelloflavone (6) and morelloflavone-7-O-glucopyranoside (7). The absolute configuration of compound 1 was assigned by circular dichroism spectroscopy as 2R, 3S. The coexistence of conformers of isolated biflavonoids in solution at 25 °C in different solvents was confirmed by variable temperature NMR studies. At room temperature (25 °C), compounds 1-7 exhibited duplicate NMR signals, while at elevated temperature (90 °C), a single set of signals was obtained. Compound 5 showed significant in vitro antioxidant activities against 1,1-diphenyl-2-picrylhydrazyl and 2,2'-azino-bis-3-ethyl benzthiazoline-6-sulfonic acid radicals. The antibacterial studies showed that compounds 5 and 6 are the most active against Staphylococcus aureus, Bacillus subtilis and Escherichia coli. Compounds 3 and 6 also showed moderate antituberculosis activity against H38 Rv. Based on the research findings, G. hombroniana could be concluded as a rich source of flavanone-flavone (3 → 8) biflavonoids that exhibit rotameric behaviour at room temperature and display significant antioxidant and antibacterial activities.

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X-ray crystallographic analysis of the compound trans-[Pt(NH2C6H11)2I2] revealed the presence of two distinct conformers within one crystal lattice. This compound was studied by variable temperature NMR spectroscopy to investigate the dynamic interconversion between these isomers. The results of this investigation were interpreted using physical (CPK) and computational (molecular mechanics and density functional theory) models. The conversion of the salts [Pt(NH2C6H11)4]X2 into trans-[Pt(NH2C6H11)2X2] (X = Cl, Br, I) was also studied and is discussed here with an emphasis on parallels to the work of Alfred Werner.