Determination of configurational isomers in polybutadienes by <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectroscopy

The NMR spectra (600 MHz) of polybutadienes containing different amounts of cis-1,4, trans- 1,4 and 1,2 units are analyzed. The critical consideration of signal assignment and the comparison of ¹H and ¹³C NMR data reveal that there are significant limitations to the quantitative characterization of polybutadienes with the use of NMR spectroscopy.     

<Superscript>1</Superscript>H and <Superscript>7</Superscript>Li NMR in defect cobaltite Li<Subscript>0.6</Subscript>CoO<Subscript>2</Subscript>

Within a temperature range of 120–330 K, ⁷Li NMR spectra in Li_0.6CoO₂ are obtained. It is shown that as the temperature increases, both smooth and stepwise variation of ⁷Li NMR contact shifts occurs. The observed effects are explained by the occupation of the excited levels of cobalt ions. The stepwise change of the resonance line width depending on the temperature is revealed. It is driven by the features of the diffusive motion of lithium ions. The calculation of the ¹H NMR line shape provides the determination of the ratio of one-, two-, and three-spin proton clusters in Li_0.6CoO₂·xH₂O.     

High-Resolution <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR of Glycyrrhizic Acid and Its Esters

Resonances for protons and C atoms in the ¹H and ¹³C NMR spectra of glycyrrhizic acid and its esters were assigned using high-resolution ¹H (600 MHz) and ¹³C (150 MHz) NMR methods. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 347–350, July–August, 2005.     

Long-range <Superscript>19</Superscript>F-<Superscript>1</Superscript>H spin-spin coupling as an indication of conformational equilibrium of fluoro-substituted aryl vinyl sulfides

Long-range ¹⁹F-¹H spin-spin coupling with participation of vinyl group protons, observed in the ¹H NMR spectra of fluoro-substituted aryl vinyl sulfides, indicates that these compounds exist as equilibrium mixtures of s-cis and s-trans rotational isomers.     

Structure of binuclear platinum(III) acetamidate complexes in solutions as probed by <Superscript>195</Superscript>Pt, <Superscript>13</Superscript>C,and <Superscript>1</Superscript>H NMR spectroscopy

¹⁹⁵Pt, ¹H, and ¹³C NMR spectroscopy was used to study the structure of binuclear platinum(III) acetamidate complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands [Pt₂(phen)₂(acam)₄](NO₃)₂ (1) and [Pt₂(bipy)₂(acam)₄](NO₃)₂ (2) in aqueous solutions. The ¹⁹⁵Pt NMR spectra of solutions of complexes 1 and 2 in D₂O exhibit two signals with satellites due to the ¹⁹⁵Pt–¹⁹⁵Pt spin-spin coupling (¹ J(Pt–Pt) ≈ 6345 Hz), whereas their ¹H and ¹³C NMR spectra contain four sets of signals for the protons and the carbon atoms of the heterocyclic and acetamidate ligands. The signals were assigned using the COSY, NOESY, and HSQC/ HMBC experiments and comparing the coordination shifts of the signals for the protons of heterocycles. These data allowed us to draw a conclusion that binuclear complexes 1 and 2 in solution have a head-to-head structure with nonequivalent platinum(III) atoms (coordination cores PtN₅ and PtN₃O₂), the axial-equatorial coordination of the bidentate heterocyclic molecules, and two bridging and two terminal acetamidate ligands.     

<Superscript>63</Superscript>Cu and <Superscript>139</Superscript>La NMR and chemical bonding in anion-deficient perovskite LACu<Subscript>0.81</Subscript>Ni<Subscript>0.19</Subscript>O<Subscript>2.5+δ</Subscript>

The ⁶³Cu and ¹³⁹La NMR spectra of the low-(δ = 0.25) and high-temperature (δ = 0) phases of lanthanum cuprate LACu_0.81Ni_0.19O_2.5+δ have been obtained. Quantum chemical calculations of the electronic structure of the high-temperature phase have been performed. It is found that the observed metal-semiconductor phase transition is attended by changes in the degree of atomic ordering and in the character of electronic conductivity over certain types of “copper” centers.     

Through space spin-spin coupling <Superscript>19</Superscript>F-<Superscript>1</Superscript>H as the base for comparative analysis of conformational equilibrium in fluorine-substituted aryl vinyl selenides and sulfides

The analysis of long-range spin-spin coupling ¹⁹F-¹H and the other conformation-dependent parameters of ¹H NMR spectra shows that aryl vinyl selenides like aryl vinyl sulfides exist as mixtures of s-cis and s-trans rotational isomers. The combined data of ¹H and ¹³C NMR spectra reveal the increase in the torsional angle ϑ at the bond X-CH=CH₂ (X = S, Se) in selenides compared to sulfides due to diminished interaction energy of the unshared electron pairs of selenium with the π*-orbitals of the double bond as compared to analogous interaction in sulfides.     

Investigation of the Structure of 5-R-3-Aryl-2,1-benzisoxazoles (Anthranils) Using <Superscript>1</Superscript>H NMR Spectroscopy

It has been shown that a feature of the ¹H NMR spectra of 5-R-3-aryl-2,1-benzisoxazoles is the large difference in chemical shift values for the H(4), H(6), and H(7) protons of the 2,1-benzisoxazole system in each of the compounds but with retention of the overall pattern for the series discussed. It was found that the effect of the heterocycle on the aryl residue in position 3 is equivalent to the effect of a moderately electron accepting group.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 732–736, May, 2005.     

<Superscript>2</Superscript>H-NMR investigation after a polymerisation-induced phase separation process*

Polymer-dispersed liquid crystals (PDLC) are composite materials consisting of micron-sized droplets of liquid crystal dispersed in a polymer matrix. The easiest method to obtain a PDLC film is the polymerisation-induced phase separation process (PIPS). The liquid crystal is mixed with a monomer of low molecular weight and polymerisation is induced by heat or UV light. The increasing molecular weight of the polymer causes the phase separation of liquid crystal from the polymer matrix as micron-sized droplets. In this work, we have studied the structural changes induced in the polymer matrix of a PDLC after the PIPS process by deuterium nuclear magnetic resonance. Two different selectively deuterated monomers have been synthesized and investigated: isobutyl methacrylate (IBMA-d₂) and methyl methacrylate (MMA-d₃). The main results were the disappearance of the characteristic two-site hop in poly-IBMA, due to liquid crystal molecules, and the lack of unreacted MMA molecules in the liquid crystal droplets. In this last case, we found that it is possible to confine temporarily the unreacted MMA molecules within liquid crystal droplets.Abbreviations MMA Methyl methacrylate - IBMA Isobutyl methacrylate - PDLC Polymer-dispersed liquid crystal - PIPS Polymerisation-induced phase separation - ²H-NMR Deuterium nuclear magnetic resonance*Dedicated to Professor V. Bertini for his 70^th birthday     

Charge distribution and mobility of lithium ions in Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> from <Superscript>6,7</Superscript>Li NMR data

A comparative analysis of ^6,7Li NMR spectra is performed for the samples of monoclinic lithium titanate obtained at different synthesis temperatures. In the ⁷Li NMR spectra three lines are found, which differ in quadrupole splitting frequencies v _Q and according to ab initio EFG calculations are assigned to three crystallographic sites of lithium: Li1 (v _Q ～ 27 kHz); Li2 (v _Q ～ 59 kHz); Li3 (v _Q ～ 6 kHz). The dynamics of lithium ions is studied in a wide temperature range from 300 K to 900 K. It is found that the narrowing of ⁷Li NMR spectra as a result of thermally activated diffusion of lithium ions in the low-temperature Li₂TiO₃ sample is observed at a higher temperature in comparison with a sample of high-temperature lithium titanate. Based on the analysis of ⁶Li NMR spectra it is assumed that there is mixed occupancy of lithium and titanium sites in the corresponding layers of the crystal structure of low-temperature lithium titanate, which hinders lithium ion transfer over regular crystallographic sites.     

Hydridosilazanes hydrolysis-condensation reactions studied by <Superscript>1</Superscript>H and <Superscript>29</Superscript>Si liquid NMR spectroscopy

Hydridosilazane compounds containing Si–N and Si–H bonds can be used as precursors of SiO_x materials. The hydrolysis-condensation reactions of tetramethyldisilazane, as a polyhydridosilazane model compound, were investigated by ¹H and ²⁹Si liquid NMR spectroscopy. These reactions were carried out at room temperature for up to 120 min in presence of water. The identified products are short linear siloxane species (hydride terminated polydimethylsiloxanes M^HD_xM^H) and cyclosiloxanes. Silicon hydride persistence in the reactional mixture suggested that silazane group is more sensitive to hydrolysis reaction than silicon hydride group. Moreover, additional experiments evidenced that the low steric hindrance of the silicon hydride influences the silazane hydrolysis kinetic. Hence the presence of ammonia released during silazane hydrolysis reaction was demonstrated to be a catalyst of the silicon hydride hydrolysis reaction.     

First-principles simulations of the <Superscript>27</Superscript>Al and <Superscript>17</Superscript>O solid-state NMR spectra of the CaAl<Subscript>2</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript> glass

The local and medium-range structure of the 20CaO·20Al₂O₃·60SiO₂ glass generated by classical molecular dynamics simulations has been compared to NMR experiments by computing the ²⁷Al and ¹⁷O NMR parameters and NMR spectra from first-principles simulations. The calculation of the NMR parameters (chemical shielding and quadrupolar parameters), which are then used to simulate solid-state MAS and 3QMAS NMR spectra, is achieved by the gauge including projector augmented-wave and the projector augmented-wave methods on the DFT-PBE relaxed structure. The NMR spectra calculated with the present approach are found to be in excellent agreement with the experimental data, providing an unambiguous view of the local and medium-range structure of aluminosilicate glasses.     

The structure of chain segments and <Superscript>1</Superscript>H NMR spectra of polychloroprene

The ¹H NMR spectra (working frequencies of 500 and 600 MHz) of polychloroprenes are studied. The spin systems of protons for monomer units of different configurations (1,2, 3,4, 1,4-cis-and 1,4- trans- units), as well as for dyad and triad combinations of 1,4 units, are classified. A high working frequency, the method of double resonance, and the calculation of chemical shifts by empirical increments make it possible to refine the assignment of ¹H NMR signals.     

Structural features of acidic fluorophosphatozirconates (hafnates) from the <Superscript>19</Superscript>F, <Superscript>31</Superscript>P, <Superscript>1</Superscript>H NMR data

Fluorophosphatometallates with the composition K₃H₃Zr₃F₃(PO₄)₅, Rb₃H₃Zr₃F₃(PO₄)₅, Rb₃H₃Hf₃F₃(PO₄)₅, CsH₂Hf₂F₂(PO₄)₃?2H₂O are studied by ³¹P, ¹⁹F, and ¹H NMR. It is found that protons enter in the composition of hydrophosphate groups and fluorine atoms occupy the terminal sites in the tetravalent metal environment. Schemes of the crystal structure of fluorophosphatometallates are proposed. It is established that in CsH₂Hf₂F₂(PO₄)₃?2H₂O water molecules are bonded to the phosphate group proton via a strong hydrogen bond and are characterized by a low energy barrier of molecular motions.     

A <Superscript>1</Superscript>H NMR study of Nile Red solvation

In order to evaluate the capabilities of NMR spectroscopy for investigation of the solvatochromic effect in luminophore solutions, the ¹H NMR chemical shifts of Nile Red in mixtures of solvents with different polarities (benzene, toluene, methanol) has been determined. Their dependence upon the solvent mixture composition has been revealed and binding sites for luminophore and solvent component molecules have been determined. The results of the NMR study are consistent with data on the fluorescence of Nile Red solutions in toluene-ethanol mixtures.     

Quantitative analysis of hydrogen peroxide by <Superscript>1</Superscript>H NMR spectroscopy

A technique utilizing ¹H NMR spectroscopy has been developed to measure the concentration of hydrogen peroxide from 10^–3 to 10 M. Hydrogen peroxide produces a peak at around 10–11 ppm, depending upon the interaction between solvent molecules and hydrogen peroxide molecules. The intensity of this peak can be monitored once every 30 s, enabling the measurement of changes in hydrogen peroxide concentration as a function of time. ¹H NMR has several advantages over other techniques: (1) applicability to a broad range of solvents, (2) ability to quantify hydrogen peroxide rapidly, and (3) ability to follow reactions forming and/or consuming hydrogen peroxide as a function of time. As an example, this analytical technique has been used to measure the concentration of hydrogen peroxide as a function of time in a study of hydrogen peroxide decomposition catalyzed by iron(III) tetrakispentafluorophenyl porphyrin.Electronic Supplementary Material Supplementary material is available for this article at     

Complete <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR signal assignments and chemical shift calculations of four 1,2,4-oxadiazole-based light-emitting liquid crystals

In this article, we describe the complete ¹H and ¹³C NMR signal assignments of four 1,2,4-oxadiazoles possessing light-emitting liquid crystal properties. These results were obtained by using one- and two-dimensional NMR techniques as well as GIAO (PCM) calculations at B3LYP/6-311++G(d,p) level for compounds 1 and 2a–d. The computed values are in good agreement with the ones obtained experimentally. In addition, some previously unexplained thermotropic features of compounds 2a–d could be clarified with the help of the geometry optimization calculations carried out by us.     

Synthesis,spectral properties,and antimicrobial activity of 2-arilamino-2,4,4,6,6-pentachloro-1,3,5,2λ<Superscript>5</Superscript>,4λ<Superscript>5</Superscript>,6λ<Superscript>5</Superscript>-triazatriphosphines and poly[bis(4-fluorophenylamino)phosphazene]

2-(4-Chloro and 4-fluorophenylamino)-2,4,4,6,6-pentachloro-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinines and poly[bis(4-fluorophenylamino)phosphazene] were synthesized by reactions of 4-fluoroaniline and 4-chloroaniline with 2,2,4,4,6,6-hexachloro-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin and poly(dichlorophosphazene), respectively, in tetrahydrofuran under argon at ?20°C, followed by heating under reflux. The products were isolated by column chromatography and were characterized by FTIR, NMR (¹H, ¹³C, ³¹P), and mass spectra, termogravimetry, and high-performance liquid chromatography. Antimicrobial activity of the monomeric compounds and polymer against 9 bacteria and 5 yeast cultures was evaluated by the disk diffusion method in dimethyl sulfoxide relative to a number of commercial antibiotics and antifungal agents. Aminophosphazene derivatives exhibited a broad spectrum of activity against both Gram-positive and Gram-negative bacterial with a magnitude comparable to reference antimicrobial agents. The polymeric product turned out to be more potent than the monomeric compounds.     

Fruit juice authentication by <Superscript>1</Superscript>H NMR spectroscopy in combination with different chemometrics tools

To discriminate orange juice from grapefruit juice in a context of fraud prevention, ¹H NMR data were submitted to different treatments to extract informative variables which were then analysed using multivariate techniques. Averaging contiguous data points of the spectrum followed by logarithmic transformation improved the results of the data analysis. Moreover, supervised variable selection methods gave better rates of classification of the juices into the correct groups. Last, independent-component analysis gave better classification results than principal-component analysis. Hence, ICA may be an efficient chemometric tool to detect differences in the ¹H NMR spectra of similar samples, and so may be useful for authentication of foods.     

Non-empirical and DFT calculations of <Superscript>19</Superscript>F and <Superscript>13</Superscript>C chemical shifts in the NMR spectra of substituted pentafluorobenzenes

Chemical shifts in ¹⁹F and ¹³C NMR spectra of substituted pentafluorobenzenes are calculated by Hartree-Fock and density functional theory methods. The calculated values are compared with the experimental data known from the literature. It is shown that chemical shifts in non-polar solvents can be predicted sufficiently accurately by the GIAO-DFT(PBE/L22) method. This method is used to predict the ¹⁹F and ¹³C chemical shifts of a heptafluorobenzyl cation in the SbF₅ medium. The best agreement between the calculated and experimental values is achieved when the counterion effect is taken into account.