35Cl NMR Research Articles

Distribution of polyelectrolytes and counterions upon polyelectrolyte complexation

HypothesisUnderstanding polyelectrolyte complexation remains limited due to the absence of a systematic methodology for analyzing the distribution of components between the polyelectrolyte complex (PEC) and the dilute phases. ExperimentsWe developed a methodology based on NMR to quantify all components of solid-like PECs and their supernatant phases formed by mixing different ratios of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid)-sodium salt (PAA). This approach allowed for determining relative and absolute concentrations of polyelectrolytes in both phases by 1H NMR studies. Using 23Na and 35Cl NMR spectroscopy we measured the concentration of counterions in both phases. FindingsRegardless of the mixing ratio of the polyelectrolytes the PEC is charge-stoichiometric, and any excess polyelectrolytes to achieve charge stoichiometry remains in the supernatant phase. The majority of counterions were found in the supernatant phase, confirming counterion release being a major thermodynamic driving force for PEC formation. The counterion concentrations in the PEC phase were approximately twice as high as in the supernatant phase. The complete mass balance of PEC formation could be determined and translated into a molecular picture. It appears that PAH is fully charged, while PAA is more protonated, so less charged, and some 10% extrinsic PAH-Cl- pairs are present in the complex.

Crystal structure of rilpivirine hydrochloride, N6H19C22Cl

A monoclinic C form of rilpivirine hydrochloride, (N6H19C22)Cl, has been obtained and characterized using solid-state 15N, 13C, and 35Cl NMR spectroscopy and multitemperature synchrotron X-ray powder diffraction. The title compound crystallizes in the monoclinic system (space group C2/c, #15) at both room (295.0(2) K) and low (100.0(2) K) temperatures. At room temperature, the following parameters are a = 19.43051(3), b = 13.09431(14), c = 17.10254(18) Å, β = 109.3937(7), V = 4104.48(9) Å3, and Z = 8. The folded molecular conformation of the cation is similar with that of free base rilpivirine with the exception of cyanovinyl group disposition. The anion links cations to infinite chains parallel to the crystallographic c axis using N–H⋯Cl bonds where both amino groups and the protonated pyrimidine ring take part in the H-bonding. The powder patterns have been submitted to the ICDD for inclusion in the Powder Diffraction File™ (PDF®).

Synthesis and morphological control of Ca5(PO4)3Cl and Ca2PO4Cl via the phase transformation of amorphous calcium phosphate in molten chlorides

In the present work, the phase conversion of amorphous calcium phosphate (ACP) in different molten chlorides (LiCl, NaCl, KCl, CaCl2) was investigated in detail. The main synthesis parameters influencing the phase purity and morphological features of the products include the chemical composition of molten salts, the heat treatment temperature and the ACP-to-flux ratio. The selective synthesis of single-phase Ca5(PO4)3Cl or Ca2PO4Cl depends on the content of CaCl2 in the reaction medium. The morphology control of Ca5(PO4)3Cl powders was achieved by varying the KCl/CaCl2 ratio in the flux, resulting in the formation of the particles of different size and shape. The KCl-rich fluxes led to the formation of relatively small nearly spherical particles, whereas the CaCl2-rich fluxes promoted an anisotropic growth of the Ca5(PO4)3Cl crystals resulting in the formation of monodispersed hexagonally-shaped microrods. Whereas the anisotropic growth was observed at relatively low temperature (750 °C) the increase of the reaction temperature up to 1200 °C significantly reduced this effect leading to the formation of the particles with obviously low aspect ratio. The phase crystallinity and purity were analyzed using powder X-ray diffraction, FTIR spectroscopy as well as 31P, 35Cl and 1H solid-state NMR. The morphological features and chemical composition of the synthesized products were studied by SEM/EDX analysis.

Confined Lewis Pairs: Investigation of the X−→Si20 Interaction in Halogen‐Encapsulating Silafulleranes

AbstractA joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si20Y20]− (X=F‐I; Y=F‐I, H, Me, Et) and ‐[Cl@Si20H12Y8]− (Y=F‐I) is presented. First, we evaluated the structure‐determining template effect of Cl− in a systematic series of concave silapolyquinane model systems. Second, we investigated the X−→Si20 interaction energy ( ) as a function of X− and Y and found the largest values for electron‐withdrawing exohedral substituents Y. Given that X− ions can be considered as Lewis bases and empty Si20Y20 clusters as Lewis acids, we classify our inseparable host–guest complexes [X@Si20Y20]− as “confined Lewis pairs”. Third, 35Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl−→Si20 interaction as the paramagnetic shielding and, in turn, (35Cl) of the endohedral Cl− ion correlate inversely with . Finally, we disclose the synthesis of [PPN][Cl@Si20Y20] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.

Confined Lewis Pairs: Investigation of the X- →Si20 Interaction in Halogen-Encapsulating Silafulleranes.

A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si20 Y20 ]- (X=F-I; Y=F-I, H, Me, Et) and -[Cl@Si20 H12 Y8 ]- (Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl- in a systematic series of concave silapolyquinane model systems. Second, we investigated the X- →Si20 interaction energy ( ) as a function of X- and Y and found the largest values for electron-withdrawing exohedral substituents Y. Given that X- ions can be considered as Lewis bases and empty Si20 Y20 clusters as Lewis acids, we classify our inseparable host-guest complexes [X@Si20 Y20 ]- as "confined Lewis pairs". Third, 35 Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl- →Si20 interaction as the paramagnetic shielding and, in turn, (35 Cl) of the endohedral Cl- ion correlate inversely with . Finally, we disclose the synthesis of [PPN][Cl@Si20 Y20 ] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.

Water dynamics in eutectic solutions of sodium chloride and magnesium sulfate: implications for life in Europa's subsurface ocean and ice shell.

Liquid water is essential for life as we know it and the coupling between water and biomolecular dynamics is crucial for life processes. Jupiter's moon Europa is a good candidate for searching for extraterrestrial life in our outer solar system, mainly because a liquid water salty ocean in contact with a rocky seafloor underlies its ice shell. Little, however, is known about the chemical composition of the subglacial ocean of Europa or the brine pockets within its ice shell and their impacts on water dynamics. Here, we employ 1H, 17O, 23Na and 35Cl NMR spectroscopy, especially NMR spin relaxation and diffusion methods, and investigate the mobility of water molecules and ions in eutectic solutions of magnesium sulfate and sodium chloride, two salts ubiquitously present on the surface of Europa, over a range of temperatures and pressures pertinent to Europa's subglacial ocean. The NMR data demonstrate the more pronounced effect of magnesium sulfate compared with sodium chloride on the mobility of water molecules. Even at its much lower eutectic temperature, the sodium chloride solution retains a relatively large level of water mobility. Our results highlight the higher potential of a sodium chloride-rich than magnesium sulfate-rich Europa's ocean to accommodate life and support life origination within the eutectic melts of Europa's ice shell.

Solid-state 35/37 Cl NMR detection of chlorine atoms directly bound to paramagnetic cobalt(II) ions in powder samples.

We report high-quality solid-state 35/37 Cl NMR spectra for chlorine atoms directly bonded to paramagnetic cobalt(II) ions (high spin S = 3/2) in powered samples of CoCl2 , CoCl2 ·2H2 O, CoCl2 ·6H2 O, and CoCl2 (terpy) (terpy = 2,2':6',2″-terpyridine). Because solid-state 35/37 Cl NMR spectra for paramagnetic cobalt(II) compounds often cover an extremely wide spectral range, they were recorded in this work in the form of variable-offset cumulative spectra. Solid-state 35/37 Cl NMR measurements were performed at three magnetic fields (11.7, 14.1, and 16.5T) and analysis of data yielded information about 35/37 Cl quadrupole coupling and hyperfine coupling tensors in these paramagnetic cobalt(II) compounds. Experimental 35/37 Cl NMR tensors were found to be in reasonable agreement with quantum chemical calculations based on a periodic DFT method implemented in BAND.

A Structurally Flexible Halide Solid Electrolyte with High Ionic Conductivity and Air Processability

AbstractIn this work, a structurally revivable, chloride‐ion conducting solid electrolyte (SE), CsSn0.9In0.067Cl3, with a high ionic conductivity of 3.45 × 10−4 S cm−1 at 25 °C is investigated. The impedance spectroscopy, density functional theory, solid‐state 35Cl NMR, and electron paramagnetic resonance studies collectively reveal that the high Cl− ionic mobility originates in the flexibility of the structural building blocks, Sn/InCl6 octahedra. The vacancy‐dominated Cl− ion diffusion encompasses co‐ordinated Sn/In(Cl) site displacements that depend on the exact stoichiometry, and are accompanied by changes in the local magnetic moments. Owing to these promising properties, the suitability of the CsSn0.9In0.067Cl3, as an electrolyte is demonstrated by designing all‐solid‐state batteries, with different anodes and cathodes. The comparative investigation of interphases with Li, Li–In, Mg, and Ca anodes reveals different levels of reactivity and interphase formation. The CsSn0.9In0.067Cl3 demonstrates an excellent humidity tolerance (up to 50% relative humidity) in ambient air, maintaining high structural integrity without compromises in ionic conductivity, which stands in contrast to commercial halide‐based lithium conductors. The discovery of a halide perovskite conductor, with air processability and structure revival ability paves the way for the development of advanced air processable SEs, for next‐generation batteries.

Choline chloride-water mixtures as new generation of green solvents: A comprehensive physico-chemical study

Natural deep eutectic solvents (NADES) are an increasingly appreciated class of mixtures composed by eco-sustainable and environmentally responsible components with hydrogen bonding (HB) donor and acceptor capabilities that enable the establishment of an extended HB network. The latter eventually leads to a substantial drop in the mixture melting point with respect to the one of the ideal mixture. Water-based NADES represent an exciting system that responds to the above mentioned criteria and contain water as a major component, rather than as an impurity or a deliberately added minor ingredient. Choline Chloride (ChCl, a well known HB acceptor in DES systems) forms NADES when mixed with water, which plays the role of HB donor. Several applications have already been identified for this system, but chemical physical properties of choline-rich mixtures, including the DES concentration, are not well established, yet. In order to overcame this limitation and introduce a subsequent, more systematic investigation of atomistic organization in these mixtures, here we report results from a series of chemical physical characterizations of water:ChCl with ratio ranging from 2 to 10 between ca. 280 and 330 K. Calorimetric measurements, density, viscosity, electric conductivity, refractive index, X-ray diffraction patterns and several 1H and 35Cl NMR spectroscopy observables are reported and compared with literature (when available). The deep eutectic nature of the water: ChCl 4:1 mixture is assessed, leading to the individuation of aquoline, as the corresponding DES. The other chemical physical properties are observed to vary, upon water content, in a monotone way, without abrupt changes across the eutectic concentration, thus providing support for the exploitation of the ChCl/water class of solvents, with tunable chemical-physical properties across their wide liquid range.

Hydrates of active pharmaceutical ingredients: A 35Cl and 2H solid-state NMR and DFT study

This study uses 35Cl and 2H solid-state NMR (SSNMR) spectroscopy and dispersion-corrected plane-wave density functional theory (DFT) calculations to characterize the molecular-level structures and dynamics of hydrates of active pharmaceutical ingredients (APIs). We use 35Cl SSNMR to measure the EFG tensors of the chloride ions to characterize hydrated forms of hydrochloride salts of APIs, along with two corresponding anhydrous forms. DFT calculations are used to refine the crystal structures of the APIs and determine relationships between the 35Cl EFG tensors and the spatial arrangements of proximate hydrogen bonds, which are particularly influenced by interactions with water molecules. We find that the relationship between 35Cl EFG tensors and local hydrogen bonding geometries is complex, but meaningful structure/property relationships can be garnered through use of DFT calculations. Specifically, for every case in which such a comparison could be made, we find that the hydrate has a smaller magnitude of CQ than the corresponding anhydrous form, indicating a chloride ion environment with a ground-state electron density of higher spherical symmetry in the former. Finally, variable-temperature 35Cl and 2H SSNMR experiments on a deuterium-exchanged sample of the API cimetidine hydrochloride monohydrate are used to monitor temperature-dependent influences on the spectra that may arise from motional influences on the 35Cl and 2H EFG tensors. From the 2H SSNMR spectra, we determine that the motions of water molecules are characterized by jump-like motions about their C2 rotational axes that occur on timescales that are unlikely to influence the 35Cl central-transition (+1/2 ↔︎ −1/2) powder patterns (this is confirmed by 35Cl SSNMR). Together, these methods show great promise for the future study of APIs in their bulk and dosage forms, especially variable hydrates in which crystallographic water content varies with external conditions such as humidity.

Stabilization of Octahedral Metal Halide Clusters by Host-Guest Complexation with γ-Cyclodextrin: Toward Nontoxic Luminescent Compounds.

γ-Cyclodextrin (γ-CD) interacts in aqueous solution with octahedral halide clusters Na2[{M6X8}Cl6] (M = Mo, W; X = Br, I) to form robust inclusion supramolecular complexes [{M6X8}Cl6@2γ-CD]2-. Single-crystal X-ray diffraction analyses revealed two conformational organizations within the adduct depending on the nature of the inner halide X within the {M6X8} core. Using 35Cl NMR and UV-vis as complementary techniques, the kinetics of the hydrolysis process were shown to increase with the following order: {W6I8} < {W6Br8} ≈ {Mo6I8} < {Mo6Br8}. The complexation with γ-CD drastically enhances the hydrolytic stability of luminescent [{M6X8}Cl6]2- cluster-based units, which was quantitatively proved by the same techniques. The resulting host-guest complexation provides a protective shell against contact with water and offers promising horizons for octahedral clusters in biology as revealed by the low dark cytotoxicity and cellular uptake.

Reducing the effects of weak homonuclear dipolar coupling with CPMG pulse sequences for static and spinning solids

The Carr-Purcell/Meiboom-Gill (CPMG) pulse sequence, initially introduced for measuring transverse relaxation time constants (T2), can provide significant signal enhancements for solid-state NMR (SSNMR) spectra. The proper implementation of CPMG for acquiring spectra influenced by chemical shift anisotropies (CSAs), first and/or second order quadrupolar interactions, or paramagnetic broadening has been well documented to date, as have the effects of heteronuclear dipolar coupling on CPMG echo trains and T2 lifetimes. Homonuclear dipolar coupling can also impact T2 lifetimes and CPMG echo trains; these effects have been thoroughly investigated for spectra of homonuclear dipolar coupled spin-1/2 nuclei typically acquired under static conditions that are predominantly influenced by dipolar broadening (e.g., 1H, 19F, etc.). In particular, it has been shown that short refocusing pulses with small flip angles can extend the effective T2 (T2eff, the observed T2 constant as impacted by experimental conditions) measured by CPMG sequences for strong homonuclear dipolar coupled spin-1/2 pairs under static conditions. To date, these effects have not been explored for (i) spin-1/2 nuclei that have significant CSAs and simultaneously feature weak homonuclear dipolar couplings, (ii) for quadrupolar nuclei that are also weakly homonuclear dipolar coupled, and (iii) for either of these cases under magic-angle spinning (MAS) conditions. Herein, we demonstrate that short refocusing pulses that cause small flip angles can reduce the attenuation of signal in CPMG echo trains resulting from dipolar dephasing caused by the weak homonuclear dipolar couplings. For both spin-1/2 and quadrupolar nuclei, this can lead to significant extensions in T2eff and signal enhancements of up to three times compared to conventional CPMG in favourable cases. These phenomena can occur under both static and magic-angle spinning (MAS) conditions, in the latter of which homonuclear couplings are reintroduced by rotational resonance (R2) recoupling. Experimental examples of 13C (I = 1/2), 2H (I = 1), 87Rb (I = 3/2), 23Na (I = 3/2), and 35Cl (I = 3/2) NMR under static and MAS conditions, as well as simulations of these phenomena, are shown and discussed.

Multinuclear NMR screening of pharmaceuticals using standardization by 2H integral of a deuterated solvent

NMR standardization approach that uses the 2H integral of deuterated solvent for quantitative multinuclear analysis of pharmaceuticals is described. As a proof of principle, the existing NMR procedure for the analysis of heparin products according to US Pharmacopeia monograph is extended to the determination of Na+ and Cl- content in this matrix. Quantification is performed based on the ratio of a 23Na (35Cl) NMR integral and 2H NMR signal of deuterated solvent, D2O, acquired using the specific spectrometer hardware. As an alternative, the possibility of 133Cs standardization using the addition of Cs2CO3 stock solution is shown. Validation characteristics (linearity, repeatability, sensitivity) are evaluated. A holistic NMR profiling of heparin products can now also be used for the quantitative determination of inorganic compounds in a single analytical run using a single sample. In general, the new standardization methodology provides an appealing alternative for the NMR screening of inorganic and organic components in pharmaceutical products.

Nutraceuticals in Bulk and Dosage Forms: Analysis by 35Cl and 14N Solid-State NMR and DFT Calculations.

This study uses 35Cl and 14N solid-state NMR (SSNMR) spectroscopy and dispersion-corrected plane-wave density functional theory (DFT) calculations for the structural characterization of chloride salts of nutraceuticals in their bulk and dosage forms. For eight nutraceuticals, we measure the 35Cl EFG tensor parameters of the chloride ions and use plane-wave DFT calculations to elucidate relationships between NMR parameters and molecular-level structure, which provide rapid NMR crystallographic assessments of structural features. We employ both 35Cl direct excitation and 1H→35Cl cross-polarization methods to characterize a dosage form containing α-d-glucosamine HCl, observe possible impurity and/or adulterant phases, and quantify the weight percent of the active ingredient. To complement this, we also investigate 14N SSNMR spectroscopy and DFT calculations to characterize nitrogen atoms in the nutraceuticals. This includes a discussion of targeted acquisition experimental protocols (i.e., acquiring a select region of the overall pattern that features key discontinuities) that allow ultrawideline spectra to be acquired rapidly, even for unreceptive samples (i.e., those with long values of T1(14N), short values of T2eff(14N), or very broad patterns). It is hoped that these experimental and computational protocols will be useful for the characterization of various solid forms of nutraceuticals (i.e., salts, polymorphs, hydrates, solvates, cocrystals, amorphous solid dispersions, etc.), help detect impurity and counterfeit solid phases in dosage forms, and serve as a foundation for future NMR crystallographic studies of nutraceutical solid forms, including studies using ab initio crystal structure prediction algorithms.

Uncovering Halogen Mixing and Octahedral Dynamics in Cs2SnX6 by Multinuclear Magnetic Resonance Spectroscopy

Cs2SnX6 (X = Cl, Br, and I) compounds have emerged as promising lead-free and ambient-stable materials for photovoltaic and optoelectronic applications. To advance these promising materials, it is crucial to determine the correlations between physical properties and their local structure and dynamics. Solid-state NMR spectroscopy of multiple NMR-active nuclei (133Cs, 119Sn, and 35Cl) in these cesium tin(IV) halides has been used to reveal the atomic structure, which plays a key role in the materials’ optical properties. The 119Sn NMR chemical shifts span approximately 4000 ppm, and the 119Sn spin-lattice relaxation times span 3 orders of magnitude when the halogen goes from chlorine to iodine in these diamagnetic compounds. Moreover, ultrawideline 35Cl NMR spectroscopy of Cs2SnCl6 indicates an axially symmetric chlorine electric field gradient tensor with a large quadrupolar coupling constant of ca. 32 MHz, suggesting the presence of a chlorine moiety that is directly attached to Sn(IV) ions. Variable-temperature 119Sn spin-lattice relaxation time measurements support the presence of dynamics of octahedral SnI6 units in Cs2SnI6. We further show that complete mixed-halide solid solutions of Cs2SnClxBr6–x and Cs2SnBrxI6–x (0 ≤ x ≤ 6) form at any halogen compositional ratio. 119Sn and 133Cs NMR spectroscopy resolve the unique local SnClnBr6–n and SnBrnI6–n (n = 0–6) octahedral and CsBrmI12–m (m = 0–12) cuboctahedral environments in the mixed-halide samples. The experimentally observed 119Sn NMR results are consistent with magnetic shielding parameters obtained by density functional theory computations that were obtained to model the random halogen distribution in mixed-halide analogues. Finally, we demonstrate the difference in the local structures and the optical absorption properties of Cs2SnI6 samples prepared by solvent-assisted and solvent-free synthesis routes.

Combinatorial enumeration of stereo, chiral and position isomers of polysubstituted halocarbons: applications to machine learning of proton and 35Cl NMR spectroscopy of halocarbons

Combinatorial enumeration of stereo, chiral and position isomers of polysubstituted halocarbons: applications to machine learning of proton and 35Cl NMR spectroscopy of halocarbons

Cl- and Na+ ions binding in slag and fly ash cement paste during early hydration as studied by 1H, 35Cl and 23Na NMR

Lacking effective and in particular direct methods, the study on Cl- and Na+ ion binding during hydration has rarely been reported. In this study, a specially developed Nuclear Magnetic Resonance setup was employed to study the Cl- and Na+ ion binding of cement pastes during hydration. Influence factors, such as slag and fly ash replacement, on the 1H, 35Cl and 23Na relaxation of the cement paste made with 1 mol/L NaCl solutions were investigated. It was found that the increase of slag in the cement gives rise to bigger pores during hydration, and the fly ash resulted in less water being consumed. The Cl- signals would first be stable then gradually decrease as a function of time. The slag in cement has minor impacts on the Cl- ions binding, and the fly ash replacement in the cement would result in less Cl- ions binding during the hydration. Results also suggest that the slag could result in later Na+ binding, and the fly ash in the cement will significantly reduce the Na+ binding. Besides, the Cl- ions will bind earlier compared to the Na+ ions, which is probably related to the characteristics of the hydrates. The normalized 35Cl and 23Na signal intensity, in general, decrease with water consumption reflecting the hydration. Furthermore, the early formed hydrates would consume relatively less water but bind more Cl- and Na- ions.

Chlorine-35 Solid-State Nuclear Magnetic Resonance Spectroscopy as an Indirect Probe of the Oxidation Number of Tin in Tin Chlorides

Ultrawideline 35Cl solid-state nuclear magnetic resonance (SSNMR) spectra of a series of 12 tin chlorides were recorded. The magnitude of the 35Cl quadrupolar coupling constant (CQ) was shown to consistently indicate the chemical state (oxidation number) of the bound Sn center. The chemical state of the Sn center was independently verified by tin Mössbauer spectroscopy. CQ(35Cl) values of >30 MHz correspond to Sn(IV), while CQ(35Cl) readings of <30 MHz indicate that Sn(II) is present. Tin-119 SSNMR experiments would seem to be the most direct and effective route to interrogating tin in these systems, yet we show that ambiguous results can emerge from this method, which may lead to an incorrect interpretation of the Sn oxidation number. The accumulated 35Cl NMR data are used as a guide to assign the Sn oxidation number in the mixed-valent metal complex Ph3PPdImSnCl2. The synthesis and crystal structure of the related Ph3PPtImSnCl2 are reported, and 195Pt and 35Cl SSNMR experiments were also used to investigate its Pt-Sn bonding. Plane-wave DFT calculations of 35Cl, 119Sn, and 195Pt NMR parameters are used to model and interpret experimental data, supported by computed 119Sn and 195Pt chemical shift tensor orientations. Given the ubiquity of directly bound Cl centers in organometallic and inorganic systems, there is tremendous potential for widespread usage of 35Cl SSNMR parameters to provide a reliable indication of the chemical state in metal chlorides.

Estimation of solid-liquid interfacial potential enabled by quantitative analysis and relaxation observation of quadrupolar NMR

Relaxation time measurements and quantitative analyses of quadrupolar nuclei via NMR were effective for the estimation of the interfacial potential at the solid-liquid interface. Moreover, quantitative nuclear magnetic resonance (qNMR) spectroscopy experiments for 23Na and 35Cl nuclei were performed. The calibration curve of the external standard aqueous NaCl solution showed excellent linearity over a considerably wide concentration range from 4 × 10−4 to 2 mol L−1 (an increase in concentration of 5000 times), with a simple experimental and analytical procedure. The relaxation time and detection rate of Cl– ions in the 35Cl NMR spectrum of a 0.10 mol L–1 NaCl aq. solution with 10 vol% α-Al2O3 drastically decreased as the zeta potential of the solid phase (ζs) of α-Al2O3 approximated a negative value. Such a result was due to the decrease in both the mobility of Cl– ions and the symmetry of the electrostatic field around 35Cl nuclei caused by the electrostatic interactions between Cl– ions and the solid surface. In the case of Na+ ions, which have a charge opposite to that of Cl– ions, the ζs dependences of the relaxation time and detection rate of Na+ ions of 23Na NMR were also opposite to those of 35Cl NMR. Particularly, such values were almost constant when ζs > 0 mV but decreased monotonically when ζs < 0 mV. It was also clarified that the counterions condensed around the vicinity of the solid phase wherein the concentration of the counterions was approximately several tens of times higher than that in the bulk phase. The estimation of electrostatic field intensities not only at solid-liquid interfaces but also at liquid-liquid interfaces and various interfaces, including those in non-aqueous solvents, can thus be performed through the proposed method.

Anisotropic magnetic excitations from single-chirality antiferromagnetic state in Ca-kapellasite

We present a $^{35}$Cl NMR study for spin $S=1/2$ perfect kagome antiferromagnet Ca-kapellasite (CaCu$_{3}$(OH)$_{6}$Cl$_{2}\cdot$0.6H$_{2}$O) with a magnetic transition at $T^{\ast}=7.2$ K. The static magnetic structure in the ground state has been determined to be a chirality-ordered $Q=0$ state, which is selected by a finite Dzyaloshinskii-Moriya interaction. The low-energy magnetic excitations in the ordered state are investigated by the nuclear spin-lattice relaxation rate measurement. We detect a weakly temperature dependent contribution in the magnetic fluctuations perpendicular to the kagome plane in addition to the dispersive spin-wave contribution in the kagome plane. The low-energy magnetic excitations from the coplanar spin structure are attributed to the zero mode originating from the flat band in this kagome antiferromagnet.