Step-by-step from amorphous phosphate to nano-structured calcium hydroxyapatite: monitoring by solid-state 1H and 31P NMR and spin dynamics.

The solid-state 1H, 31P NMR spectra and cross-polarization (CP MAS) kinetics in the series of samples containing amorphous phosphate phase (AMP), composite of AMP + nano-structured calcium hydroxyapatite (nano-CaHA) and high-crystalline nano-CaHA were studied under moderate spinning rates (5-30 kHz). The combined analysis of the solid-state 1H and 31P NMR spectra provides the possibility to determine the hydration numbers of the components and the phase composition index. A broad set of spin dynamics models (isotropic/anisotropic, relaxing/non-relaxing, secular/semi-non-secular) was applied and fitted to the experimental CP MAS data. The anisotropic model with the angular averaging of dipolar coupling was applied for AMP and nano-CaHA for the first time. It was deduced that the spin diffusion in AMP is close to isotropic, whereas it is highly anisotropic in nano-CaHA being close to the Ising-type. This can be caused by the different number of internuclear interactions that must be explicitly considered in the spin system for AMP (I-S spin pair) and nano-CaHA (IN-S spin system with N ≥ 2). The P-H distance in nano-CaHA was found to be significantly shorter than its crystallographic value. An underestimation can be caused by several factors, among those - proton conductivity via a large-amplitude motion of protons (O-H tumbling and the short-range diffusion) that occurs along OH- chains. The P-H distance deduced for AMP, i.e. the compound with HPO42- as the dominant structure, is fairly well matched to the crystallographic data. This means that the CP MAS kinetics is a capable technique to obtain complementary information on the proton localization in H-bonds and the proton transfer in the cases where traditional structure determination methods fail.

CP MAS kinetics in soft matter: Spin diffusion, local disorder and thermal equilibration in poly(2-hydroxyethyl methacrylate).

The 1H-13C cross-polarization magic angle spinning kinetics was studied in poly(2-hydroxyethyl methacrylate) (pHEMA), i.e. a soft material with high degrees of internal freedom and molecular disorder, having the purpose to track the influence of increasing local incoherent contributions to the effects of coherent nature in the open quantum spin systems. The experimental CP MAS kinetic curves were analyzed in the frame of the models of isotropic and anisotropic spin diffusion with thermal equilibration. The rates of spin diffusion and spin-lattice relaxation as well as the profiles of distribution of dipolar coupling, the parameters accounting the effective size of spin clusters and the local order parameters were determined. The intensities of the peaks of periodic quasi-equilibrium origin gradually decrease with increasing disorder, i.e. going from most ordered to more disordered sites in the polymer. Assuming that the thermal motion induced by the temperature gradients is much faster than the equilibration driven by spin diffusion due the difference in spin temperatures, it was deduced that the thermal equilibration in pHEMA occurs in the time scale of 10-4 s. This is one order of magnitude faster than the spectral spin diffusion, which occurs between spins having different resonance frequencies. The thermal equilibration in the case of remote spin clusters was described by the 'stretched exponent' decay. This led to the fractal dimension Dp ≈ 1.65 for both carbon sites (quaternary and carbonyl). The obtained Dp value corresponds to the aggregates, which images are very similar to those for pHEMA and some other related polymer structures are usually conceived.

Molecular aggregation in liquid acetic acid: insight from molecular dynamics/quantum mechanics modelling of structural and NMR properties.

The 1H NMR signal of the acidic proton in acetic acid molecules shows a marked upfield shift in the neat liquid as compared to that in low-concentration acetic acid solution in inert solvents where acetic acid cyclic dimers predominate. The underlying reasons for this phenomenon are analyzed in this work by considering classical molecular dynamics simulations and combined quantum mechanics/molecular mechanics calculations of the 1H NMR chemical shift of the acidic proton in the neat liquid and in the cyclic dimer of acetic acid in cyclohexane solution. Recorded trajectories were quantitatively analyzed in terms of different types of molecular aggregates formed in the neat liquid by using a geometrical definition of the hydrogen bond. Both the geometrical analysis and the computational NMR results indicate that the cyclic dimer cannot be the dominating aggregation pattern for acetic acid molecules in the neat liquid. The applied computational approach reproduces the lowering of the 1H NMR chemical shift of the acidic proton in acetic acid when going from cyclohexane solution to the neat liquid very well. The presence of acetic acid aggregates with hydrogen bonding between hydroxyl moieties and of monomeric acetic acid molecules in the neat liquid is found to lead to the observed lowering of the chemical shift, with lesser contribution from the formation of open acetic acid aggregates.

Electron paramagnetic resonance of a copper doped [(CH3)2NH2][Zn(HCOO)3] hybrid perovskite framework.

We report a continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) as well as pulse electron nuclear double resonance (ENDOR) study of Cu2+ doped [(CH3)2NH2][Zn(HCOO)3] hybrid perovskite which exhibits a structural phase transition. The multifrequency (X, Q and W-band) CW EPR measurements allow the temperature evolution of the Cu2+ ion local environment to be studied. The spectrum of the ordered (low-temperature) phase reveals an axially distorted octahedral Cu2+ site confirming the successful replacement of the Zn2+ ions and formation of the CuO6 octahedra. The CW EPR spectrum of the disordered (high-temperature) phase shows an additional broad line which gradually diminishes on cooling. The EPR linewidth of the axially symmetric Cu2+ ion site exhibits an anomaly at the phase transition point and Arrhenius-type behavior in the disordered phase. The temperature dependent Cu2+ spin Hamiltonian parameters change abruptly at the phase transition point indicating a strong first-order character of the transition. The X-band pulse ENDOR spectrum of the ordered phase reveals several protons in the vicinity of the Cu2+ center.

Aqueous acidities of primary benzenesulfonamides: Quantum chemical predictions based on density functional theory and SMD.

Aqueous pK(a) of selected primary benzenesulfonamides are predicted in a systematic manner using density functional theory methods and the SMD solvent model together with direct and proton exchange thermodynamic cycles. Some test calculations were also performed using high-level composite CBS-QB3 approach. The direct scheme generally does not yield a satisfactory agreement between calculated and measured acidities due to a severe overestimation of the Gibbs free energy changes of the gas-phase deprotonation reaction by the used exchange-correlation functionals. The relative pK(a) values calculated using proton exchange method compare to experimental data very well in both qualitative and quantitative terms, with a mean absolute error of about 0.4 pK(a) units. To achieve this accuracy, we find it mandatory to perform geometry optimization of the neutral and anionic species in the gas and solution phases separately, because different conformations are stabilized in these two cases. We have attempted to evaluate the effect of the conformer-averaged free energies in the pK(a) predictions, and the general conclusion is that this procedure is highly too costly as compared with the very small improvement we have gained.

Probing structural and dynamic properties of MAPbCl3 hybrid perovskite using Mn2+ EPR.

Hybrid methylammonium (MA) lead halide perovskites have emerged as materials exhibiting excellent photovoltaic performance related to their rich structural and dynamic properties. Here, we use multifrequency (X-, Q-, and W-band) electron paramagnetic resonance (EPR) spectroscopy of Mn2+ impurities in MAPbCl3 to probe the structural and dynamic properties of both the organic and inorganic sublattices of this compound. The temperature dependent continuous-wave (CW) EPR experiments reveal a sudden change of the Mn2+ spin Hamiltonian parameters at the phase transition to the ordered orthorhombic phase indicating its first-order character and significant slowing down of the MA cation reorientation. Pulsed EPR experiments are employed to measure the temperature dependences of the spin-lattice relaxation T1 and decoherence T2 times of the Mn2+ ions in the orthorhombic phase of MAPbCl3 revealing a coupling between the spin center and vibrations of the inorganic framework. Low-temperature electron spin echo envelope modulation (ESEEM) experiments of the protonated and deuterated MAPbCl3 analogues show the presence of quantum rotational tunneling of the ammonium groups, allowing to accurately probe their rotational energy landscape.

A quantum mechanics/molecular dynamics study of electric field gradient fluctuations in the liquid phase. The case of Na+ in aqueous solution.

The (23)Na quadrupolar coupling constant of the Na(+) ion in aqueous solution has been predicted using molecular dynamics simulations and hybrid quantum mechanics/molecular mechanics methods for the calculation of electric field gradients. The developed computational approach is generally expected to provide reliable estimates of the quadrupolar coupling constants of monoatomic species in condensed phases, and we show here that intermolecular polarization and non-electrostatic interactions are of crucial importance as they result in a 100% increased quadrupolar coupling constant of the ion as compared to a simpler pure electrostatic picture. These findings question the reliability of the commonly applied classical Sternheimer approximation for the calculations of the electric field gradient. As it can be expected from symmetry considerations, the quadrupolar coupling constants of the 5- and 6-coordinated Na(+) ions in solution are found to differ significantly.

NMR spin-spin coupling constants in polymethine dyes as polarity indicators.

Herein, we explore the use of spin-spin coupling constants (SSCCs) in merocyanine (MCYNE) dyes as indicators of polarity. For this purpose, we use Car-Parrinello hybrid quantum mechanics/molecular mechanics (QM/MM) to determine the structures of MCYNE in solvents of different polarity, followed by computations of the SSCCs by using QM/MM linear-response theory. The molecular geometry of MCYNE switches between neutral, cyanine-like, and zwitterionic depending on the polarity of the solvent. This structural variation is clearly reflected in the proton SSCCs in the polymethine backbone, which are highly sensitive to the dielectric nature of the environment; this mechanism can be used as a "polarity indicator" for different microenvironments. This result is highlighted by computing the SSCCs of the MCYNE probe in the cavity of the beta-lactoglobulin protein. The computed SSCCs clearly indicate a non-polar hydrophobic dielectric nature of this cavity.

Hydrogen bonding in pyridine N-oxide/acid systems: proton transfer and fine details revealed by FTIR, NMR, and X-ray diffraction.

The H-bonded complexes of pyridine N-oxide (PyO) with H(2)O, acetic, cyanoacetic, propiolic, tribromoacetic, trichloroacetic, trifluoroacetic, hydrochloric, and methanesulfonic acids have been studied by FTIR and NMR spectroscopy, X-ray diffraction, and quantum chemical DFT calculations. Correlations between vibrational frequencies of the NO stretching and PyO ring modes and geometric parameters of the H-bond have been established. FTIR experiments show and DFT calculations confirm that definite discontinuity is present in the vicinity of the midpoint in the proton transfer pathway. The established correlations significantly aid in the understanding of fine effects such as the isotope (deuteration) effect, crystal-to-solution transition, or criticality of aqueous solutions induced by ionic pairs. Geometric isotope effect in the ionic H-bond aggregate of PyO·H(D)Cl was found to be extraordinary large. Measured FTIR, CP/MAS, and high-resolution (13)C NMR spectra indicate that H-bond in the PyO·HCl complex in polar solvent can potentially be more ionic than in the crystal. Vibrational modes of ionic pairs originating via proton transfer in H-bond complexes can provide new information concerning the interionic interaction and its role in the phase separation and mezo-structuring processes. The results are compared to the relevant data for PyO·HCl complex in argon matrix.

Computational protocols for prediction of solute NMR relative chemical shifts. a case study of L-tryptophan in aqueous solution.

In this study, we have applied two different spanning protocols for obtaining the molecular conformations of L-tryptophan in aqueous solution, namely a molecular dynamics simulation and a molecular mechanics conformational search with subsequent geometry re-optimization of the stable conformers using a quantum mechanically based method. These spanning protocols represent standard ways of obtaining a set of conformations on which NMR calculations may be performed. The results stemming from the solute-solvent configurations extracted from the MD simulation at 300 K are found to be inferior to the results stemming from the conformations extracted from the MM conformational search in terms of replicating an experimental reference as well as in achieving the correct sequence of the NMR relative chemical shifts of L-tryptophan in aqueous solution. We find this to be due to missing conformations visited during the molecular dynamics run as well as inaccuracies in geometrical parameters generated from the classical molecular dynamics simulations.

Solid-State NMR and Impedance Spectroscopy Study of Spin Dynamics in Proton-Conducting Polymers: An Application of Anisotropic Relaxing Model.

The 1H-13C cross-polarization (CP) kinetics in poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMETAC) was studied under moderate (10 kHz) magic-angle spinning (MAS). To elucidate the role of adsorbed water in spin diffusion and proton conductivity, PMETAC was degassed under vacuum. The CP MAS results were processed by applying the anisotropic Naito and McDowell spin dynamics model, which includes the complete scheme of the rotating frame spin-lattice relaxation pathways. Some earlier studied proton-conducting and nonconducting polymers were added to the analysis in order to prove the capability of the used approach and to get more general conclusions. The spin-diffusion rate constant, which describes the damping of the coherences, was found to be strongly depending on the dipolar I-S coupling constant (DIS). The spin diffusion, associated with the incoherent thermal equilibration with the bath, was found to be most probably independent of DIS. It was deduced that the drying scarcely influences the spin-diffusion rates; however, it significantly (1 order of magnitude) reduces the rotating frame spin-lattice relaxation times. The drying causes the polymer hardening that reflects the changes of the local order parameters. The impedance spectroscopy was applied to study proton conductivity. The activation energies for dielectric relaxation and proton conductivity were determined, and the vehicle-type conductivity mechanism was accepted. The spin-diffusion processes occur on the microsecond scale and are one order faster than the dielectric relaxation. The possibility to determine the proton location in the H-bonded structures in powders using CP MAS technique is discussed.

Structural Features of the [C4mim][Cl] Ionic Liquid and Its Mixtures with Water: Insight from a 1H NMR Experimental and QM/MD Study.

The 1H NMR chemical shift of water exhibits non-monotonic dependence on the composition of an aqueous mixture of 1-butyl-3-methylimidazolium chloride, [C4mim][Cl], ionic liquid (IL). A clear minimum is observed for the 1H NMR chemical shift at a molar fraction of the IL of 0.34. To scrutinize the molecular mechanism behind this phenomenon, extensive classical molecular dynamics simulations of [C4mim][Cl] IL and its mixtures with water were carried out. A combined quantum mechanics/molecular mechanics approach based on the density functional theory was applied to predict the NMR chemical shifts. The proliferation of strongly hydrogen-bonded complexes between chloride anions and water molecules is found to be the reason behind the increasing 1H NMR chemical shift of water when its molar fraction in the mixture is low and decreasing. The model shows that the chemical shift of water molecules that are trapped in the IL matrix without direct hydrogen bonding to the anions is considerably smaller than the 1H NMR chemical shift predicted for the neat water. The structural features of neat IL and its mixtures with water have also been analyzed in relation to their NMR properties. The 1H NMR spectrum of neat [C4mim][Cl] was predicted and found to be in very reasonable agreement with the experimental data. Finally, the experimentally observed strong dependence of the chemical shift of the proton at position 2 in the imidazolium ring on the composition of the mixture was rationalized.

On the existence of the H3 tautomer of adenine in aqueous solution. Rationalizations based on hybrid quantum mechanics/molecular mechanics predictions.

The (15)N NMR spectrum of adenine in aqueous solution has been modeled using high-level combined density functional theory/molecular mechanics techniques coupled to a dynamical averaging scheme. The explicit consideration of the three lowest-energy tautomers of adenine-H9, H7 and H3-allows for a well-founded comparison to experimental data. Based on a very good agreement between the predicted and measured (15)N NMR spectrum of adenine, we have estimated the populations of the H9 and H7 tautomers to be around 83 and 17%, respectively-in good agreement with experimental data-and thus concluded that the H3 tautomer is likely not to be formed in aqueous solution. In addition to the (15)N NMR spectrum we have also predicted the (13)C NMR spectrum and (2)J((15)N-H) indirect spin-spin coupling constants. Finally we have calculated and rationalized the general shape of the low-resolution UV absorption spectrum of adenine in water.

NMR and quantum chemistry study of mesoscopic effects in ionic liquids.

(1)H, (13)C, and (81)Br NMR spectra of the neat room-temperature ionic liquid (RTIL), namely, 1-decyl-3-methyl-imidazolium bromide ([C(10)mim][Br]) as well as its solutions in acetonitrile, dichloromethane, methanol, and water have been investigated. The most important observation of the present work is the significant broadening of (81)Br NMR signal in the solutions of [C(10)mim][Br] in organic solvents, which molecules tend to associate into hydrogen bond networks and the appearance of the complex contour of (81)Br NMR signal in the neat RTIL as well as in the liquid crystalline (LC) ionogel formed in RTIL/water solution. The complex structure of (81)Br signal changes upon heating and dilution in water. It disappears at ca. 353 K and in the aqueous solution below ca. 0.1 mol fraction of RTIL. Several new (1)H NMR signals appear at the [C(10)mim][Br]/water compositions just before the solidification of the sample (approximately 0.3 mol fraction of [C(10)mim][Br]). These additional peaks can be attributed to the H(2)O protons placed in inhomogeneous regions of the sample or due to the appearance of nonequivalent water sites in LC ionogel, the exchange between which is highly restricted or even frozen. The complex shape of (81)Br NMR signal can originate from the presence of supra-molecular structures (mesoscopic domains) that live over the period of the NMR time-scale due to a very high viscosity of [C(10)mim][Br]. These domains exhibit some features of partially disordered solids (liquid- or plastic crystals). To evaluate the static and dynamic contributions into the relaxation rate of (81)Br nuclei, the quantum chemistry calculations of the electronic structure, magnetic shielding, and electric field gradient (EFG) tensors of [C(10)mim][Br] and related model systems (Br(-).6H(2)O cluster, with addition of the dipoles (hydrogen fluoride) and charged particles - cations: H(+) or C(1)mim(+)) were performed.

Computational NMR Study of Ion Pairing of 1-Decyl-3-methyl-imidazolium Chloride in Molecular Solvents.

The 1H NMR spectra of 10-5 mole fraction solutions of 1-decyl-3-methyl-imidazolium chloride ionic liquid in water, acetonitrile, and dichloromethane have been measured. The chemical shift of the proton at position 2 in the imidazolium ring of 1-decyl-3-methyl-imidazolium (H2) is rather different for all three samples, reflecting the shifting equilibrium between the contact pairs and free fully solvated ions. Classical molecular dynamics simulations of the 1-decyl-3-methyl-imidazolium chloride contact ion pair as well as of free ions in water, acetonitrile, and dichloromethane have been conducted, and the quantum mechanics/molecular mechanics methods have been applied to predict NMR chemical shifts for the H2 proton. The chemical shift of the H2 proton was found to be primarily modulated by hydrogen bonding with the chloride anion, while the influence of the solvents-though differing in polarity and capabilities for hydrogen bonding-is less important. By comparing experimental and computational results, we deduce that complete disruption of the ionic liquid into free ions takes place in an aqueous solution. Around 23% of contact ion pairs were found to persist in acetonitrile. Ion-pair breaking into free ions was predicted not to occur in dichloromethane.

NMR and DFT study on media effects on proton transfer in hydrogen bonding: concept of molecular probe with an application to ionic and super-polar liquids.

Media effects of ionic and super-polar liquids on the state of H-bonding were studied by NMR and DFT methods. The proton sharing (positioning) in the H-bond was monitored following the chemical shifts of picolinic acid N-oxide (PANO) used as the molecular probe. The relationships between PANO 1H and 13C chemical shifts and proton position in the O-H...O bridge were calibrated using traditional organic solvents and other H-bond complexes of pyridine N-oxide with acids to increase the H-bond strength. A reliable parameter for H-bond monitoring was proposed. The state of the H-bond in ionic liquid media is largely governed by the dielectric properties of the bulk media. A drastic fall-out of PANO/[BuMePyr][TfO] from the general dielectric scheme built using solvents with increasing dielectric constant (from chloroform to water and culminating with formamide) was observed. On a molecular level this effect indicates that the ionic liquid [BuMePyr][TfO] can act on H-bonded systems as a stimulant of proton transfer. In 'super-polar' media (formamide) the intramolecular H-bond system converts into an intermolecular one forming a neutral H-bond complex of PANO with the formamide molecule.

Prediction of spin-spin coupling constants in solution based on combined density functional theory/molecular mechanics.

We present theory and implementation of calculation of spin-spin coupling constants within combined quantum mechanics/molecular mechanics methods. Special attention is given to the role of explicit solvent polarization as well as the molecular consequences due to hydrogen bonding. The model is generally applicable but is here implemented for the case of density functional theory. First applications to liquid water and acetylene in aqueous solution are presented. Good agreement between theory and experiment is obtained in both cases, thereby showing the strength of our approach. Finally, spin-spin coupling constants across hydrogen bonds are discussed considering for the first time the role of an explicit solvent on this class of spin-spin couplings.

NMR, Raman, and DFT Study of Lyotropic Chromonic Liquid Crystals of Biomedical Interest: Tautomeric Equilibrium and Slow Self-Assembling in Sunset Yellow Aqueous Solutions.

Temperature and composition effects in Sunset Yellow FCF (SSY) aqueous solutions were studied by the 1H, 15N NMR as well as Raman spectroscopy passing through all phase transitions between isotropic phase (I) and chromonic phases-nematic (N) and columnar (M). It was shown that the tautomeric equilibrium in SSY is strongly shifted toward the hydrazone form. The corresponding equilibrium constant p KT = 2.5 was deduced using the density functional theory solvent model density model. The dominance of the hydrazone form was confirmed experimentally using the long-range 1H-15N correlation, widely known as heteronuclear multiple bond correlation. The peak found in the 1H NMR spectra at ca. 14.5 ppm can be attributed to the proton in the intramolecular N-H···O bond. The existence of this signal shows that (i) the growth of the SSY aggregates is accompanied by the segregation of water in the intercolumnar areas with no access for exchange with the N-H protons in the internal layers of the columnar stacks and that (ii) the lifetime of those aggregates is ≥10-8 s or even longer. The temperature dependences of H2O chemical shift and Raman O-H stretching band shape show that water confined in the intercolumnar areas behaves as in the neat substance. When the sample is heated and the transition from M phase to N phase occurs, the molecular motion of water is seen to change in a manner similar to that when water is melting. The equilibration time for N + M→ M is very long because of slow supramolecular restructuring, i.e., the growing of columnar stacks and building of hexagonal arrays. If the sample is cooled down to the temperature below N → M transition relatively fast, the structural changes are behind, and the system falls into supercooled state. In this case, the system evolves via long-lasting self-assembling from the supercooled state to the equilibrium. This process affects the shape of the 1H NMR signal and is easy to monitor.

Determination of critical indices by "slow" spectroscopy: NMR shifts by statistical thermodynamics and density functional theory calculations.

The temperature dependencies of NMR shifts in the critical region of two coexisting phases have been simulated using statistical thermodynamics and graph-theory consideration of equilibrium processes of molecular association. Microparameters of magnetic screening of various water and water/pyridine structures used in the statistical averaging have been evaluated by density functional theory calculations (PBE1PBE and B3PW91 functionals in the 6-311++G** basis set). The gauge-including atomic orbital (GIAO) approach has been applied to ensure gauge invariance of the results. Solvent effects were taken into account by a polarized continuum model (PCM). NMR shifts "order parameters" (Deltadelta = |delta+ - delta-|) and "diameters" (phidelta = |(delta+ + delta-)/2 - deltaC|, where delta+, delta-, and deltaC are the chemical shifts of coexisting phases and at the critical point respectively) have been calculated in each case close to the lower critical solution point (TL) and processed using linear regression analysis of Deltadelta approximately |T - TL| and phidelta approximately |T - TL| in the log-log plot. It has been shown that the critical index beta can be evaluated with high precision from the slope of Deltadelta = f(T - TL) at any realistic set of model input parameters. The slope of diameter has been found to depend on both input beta and alpha values. The obtained phidelta slopes (0.58-0.63) are very close to 2beta values. The results are discussed within the concept of complete scaling. Results of simulation are compared and supported by experimental NMR data for water/2,6-lutidine, acetic anhydride/n-heptane, and acetic anhydride/cyclohexane systems.

1H NMR and DFT study of proton exchange in heterogeneous structures of pyridine-N-oxide/HCl/DCl/H2O.

Moderately narrow 1H NMR signals were observed in the solid-phase obtained from pyridine-N-oxide (PyO)...HCl solutions in acetonitrile/H2O after heterogeneous phase separation. High-resolution 1H NMR spectra are compared with those of crystalline PyO...HCl and PyO...DCl. It is concluded that partially resolved peaks in 1H NMR spectra of solids are related with heterogeneity of the spin system and the presence of different mobile H-bond clusters containing PyO, HCl, DCl and water molecules. Some part of non-bonded water or HCl molecules is captured in the cavities of crystalline samples. The attribution of the 1H NMR signals was based on the density functional theory calculation of proton magnetic screening tensor of the most expected H-bond structures in the 6-311G** basis taking into account the solvent effect by the polarized continuum model.