1H MAS Research Articles

Advanced Nuclear Magnetic Resonance, Fourier Transform–Infrared, Visible-NearInfrared and X-ray Diffraction Methods Used for Characterization of Organo-Mineral Fertilizers Based on Biosolids

Biosolids from stabilized sludge present a high fertilization potential, due to their rich content of nutrients and organic matter. The intrinsic and subtle properties of such fertilizers may greatly influence the fertilization efficiency. In this sense, the utility, advantages and limitations of advanced characterization methods, for the investigation of structural and dynamic properties at the microscopic scale of slightly different formulations of fertilizers were assessed. For that, three formulas of organo-mineral fertilizers based on biosolids (V1, V2 and V3), having at least 2% N, 2% P2O5, and 2% K2O, were characterized by advanced methods, such as 1H NMR relaxometry, 1H MAS and 13C CP-MAS NMR spectroscopy, 1H double-quantum NMR and FT-IR spectroscopy. Advanced structural characterization was performed using SEM, EDX and X-ray diffraction. Four dynamical components were identified in the NMR T2 distribution showing that the rigid component has a percentage larger than 90%, which explains the broad band of NMR spectra confirmed by the distributions of many components in residual dipolar coupling as were revealed by 1H DQ-NMR measurements. SEM and EDX measurements helped the identification of components from crystalline-like X-ray diffraction patterns. To evaluate the release properties of organo-mineral fertilizers, dynamic measurements of classical electric conductivity and pH were performed by placing 0.25 g of the formulas (V1, V2 and V3) in 200 mL of distilled water. The content of N and P were quantified using specific reactants, combined with VIS-nearIR spectroscopy. Two release mechanisms were observed and characterized. It was found that V3 presents the smallest release velocity but releases the largest number of fertilizers.

Structure of vanadia-titania catalysts doped with alkali metals according to solid-state NMR, ESR spectroscopies and DFT

In this work, V/M/TiO2 catalysts (M = Li, Na, K, Rb and Cs) were investigated with Solid-state nuclear magnetic resonance (SSNMR), electron paramagnetic resonance (ESR) and first-principles calculations. The total vanadium content corresponds to half monolayer (4 V atoms·nm−2 of TiO2 support surface), with V/M atomic ratio being 4/0.6. Static 51V and MAS 1H, 7Li, 51V, 23Na, 133Cs NMR spectra were acquired. Surface moieties of vanadium oxide on (001) anatase surface were modeled using density functional theory (DFT); their 51V NMR parameters were calculated with the Gauge-Including Projected Augmented Wave (GIPAW) method and compared to experimental data obtained with 51V SSNMR spectroscopy. It was found that mainly strongly bound vanadium sites (V3) are formed on anatase samples, located on TiO2 terminal oxygen atoms. Weakly bound vanadium sites (V1, V2) are formed on bridged anatase oxygen atoms. Supported alkali metals (Li, Na, K, Rb and Cs) on TiO2 were found to interact with protons located on the terminal and bridged TiO2 oxygen atoms. The relative ratio of weakly bound vanadium sites (V1, V2) increased on alkali-containing samples. Calculations performed showed lithium cation to prefer V-O-Ti or V-O-V bonds over VO, unsystematically deshielding vanadium nuclei. The presence of V3+ is likely to cause a loss of intensity in 51V NMR spectra.

Leucopterin, the white pigment in butterfly wings: structural analysis by PDF fit, FIDEL fit, Rietveld refinement, solid-state NMR and DFT-D.

Leucopterin (C6H5N5O3) is the white pigment in the wings of Pieris brassicae butterflies, and other butterflies; it can also be found in wasps and other insects. Its crystal structure and its tautomeric form in the solid state were hitherto unknown. Leucopterin turned out to be a variable hydrate, with 0.5 to about 0.1 molecules of water per leucopterin molecule. Under ambient conditions, the preferred state is the hemihydrate. Initially, all attempts to grow single crystals suitable for X-ray diffraction were to no avail. Attempts to determine the crystal structure by powder diffraction using the direct-space method failed, because the trials did not include the correct, but rare, space group P2/c. Attempts were made to solve the crystal structure by a global fit to the pair distribution function (PDF-Global-Fit), as described by Prill and co-workers [Schlesinger et al. (2021). J. Appl. Cryst. 54, 776-786]. The approach worked well, but the correct structure was not found, because again the correct space group was not included. Finally, tiny single crystals of the hemihydrate could be obtained, which allowed at least the determination of the crystal symmetry and the positions of the C, N and O atoms. The tautomeric state of the hemihydrate was assessed by multinuclear solid-state NMR spectroscopy. 15N CPMAS spectra showed the presence of one NH2 and three NH groups, and one unprotonated N atom, which agreed with the 1H MAS and 13C CPMAS spectra. Independently, the tautomeric state was investigated by lattice-energy minimizations with dispersion-corrected density functional theory (DFT-D) on 17 different possible tautomers, which also included the prediction of the corresponding 1H, 13C and 15N chemical shifts in the solid. All methods showed the presence of the 2-amino-3,5,8-H tautomer. The DFT-D calculations also confirmed the crystal structure. Heating of the hemihydrate results in a slow release of water between 130 and 250 °C, as shown by differential thermal analysis and thermogravimetry (DTA-TG). Temperature-dependent powder X-ray diffraction (PXRD) showed an irreversible continuous shift of the reflections upon heating, which reveals that leucopterin is a variable hydrate. This observation was also confirmed by PXRD of samples obtained under various synthetic and drying conditions. The crystal structure of a sample with about 0.2 molecules of water per leucopterin was solved by a fit with deviating lattice parameters (FIDEL), as described by Habermehl et al. [Acta Cryst. (2022), B78, 195-213]. A local fit, starting from the structure of the hemihydrate, as well as a global fit, starting from random structures, were performed, followed by Rietveld refinements. Despite dehydration, the space group remains P2/c. In both structures (hemihydrate and variable hydrate), the leucopterin molecules are connected by 2-4 hydrogen bonds into chains, which are connected by further hydrogen bonds to neighbouring chains. The molecular packing is very efficient. The density of leucopterin hemihydrate is as high as 1.909 kg dm-3, which is one of the highest densities for organic compounds consisting of C, H, N and O only. The high density might explain the good light-scattering and opacity properties of the wings of Pieris brassicae and other butterflies.

Characterization of Monochromate and Hemichromate AFm Phases and Chromate-Containing Ettringite by 1H, 27Al, and 53Cr MAS NMR Spectroscopy

The calcium aluminate hydrate AFm and AFt phases formed upon hydration of Portland cement have an important role in the stabilization and solidification of hazardous chromate ions in hardened cement. AFm monochromate (Ca4[Al(OH)6]2(CrO4)·12H2O), AFm hemichromate (Ca4[Al(OH)6]2(CrO4)0.5(OH)·12H2O) and the chromate-containing AFt phase, Ca6[Al(OH)6]2-(CrO4)3·24H2O, were synthesized and investigated by 1H, 27Al, and 53Cr MAS NMR spectroscopy. 27Al quadrupolar coupling parameters (CQ, ηQ) and isotropic chemical shifts (δiso) were determined for the three phases, including two distinct Al sites in chromate-AFt, as observed by 27Al MAS and MQMAS NMR. Two dominant peaks are apparent in the 1H MAS NMR spectra of each of the phases. For the AFm phases, these resonances are assigned to framework hydroxyl groups (1.7–2.0 ppm) and water molecules/hydroxyls (5.0–5.5 ppm) in the interlayer. For chromate-AFt, the peaks are ascribed to framework hydroxyl groups in the [Ca6Al2(OH)12]6+ columns (~1.4 ppm) and water molecules (~4.8 ppm) associated with the Ca ions. 53Cr MAS NMR spectra acquired at 22.3 T for the samples show a narrow resonance for both chromate AFm phases, whereas indications of three distinct Cr resonances are apparent for the chromate AFt. The absence of any second-order quadrupolar effects in the 53Cr NMR spectra strongly suggests that the chromate ions are highly mobile in the anionic sites of the AFm and AFt structures. The NMR data reported in this work are in agreement with the reported crystal structures for the chromate AFm and AFt phases and may be useful for identification and characterization of chromate fixation in cementitious systems, complementing information gained from conventional powder X-ray diffraction studies.

Composites Containing Nanohydroxyapatites and a Stable TEMPO Radical: Preparation and Characterization Using Spectrophotometry, EPR and 1H MAS NMR

Hydroxyapatite is the main constituent of mammalian hard tissues. Basic applications of synthetic hydroxyapatites include bone and dental implantology and drug delivery systems. The study of hydroxyapatite surface properties could give greater insight into the processes of bone mineralization and degradation. Nitroxide radicals are stable radicals that exhibit anticancer and antioxidative properties and are often used as spin probes to study the dynamics of complex biological systems. In this work, we attempted to adsorb the stable 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) on two hydroxyapatites (HAs) differing in specific surface area and the degree of hydration. The adsorption was carried out from cyclohexane, 1-chlorobutane and water. The solutions after adsorption were studied spectrophotometrically, while the obtained composites were characterized via NMR and EPR spectroscopy. The results show that it is possible to reproducibly obtain fairly stable composites, where the main factors influencing the adsorbed amount of the radical are solvent polarity and specific surface area of hydroxyapatite. The Langmuir isotherm was determined to be the most suitable adsorption model. The analysis of EPR and NMR spectra allowed us to determine the distribution of the TEMPO molecules on the hydroxyapatite surface, as well as a probable adsorption mechanism. The HA/TEMPO composites could potentially be used to study certain properties of hydroxyapatite surfaces with EPR spectroscopy. They could also be used as fillers after hard tissue surgery, as well as metal-free MRI contrasts.

Formation and local structure of framework Al Lewis sites in beta zeolites.

Framework AlFR Lewis sites represent a substantial portion of active sites in H-BEA zeolite catalysts activated at low temperatures. We studied their nature by 27Al WURST-QCPMG nuclear magnetic resonance (NMR) and proposed a plausible mechanism of their formation based on periodic density functional theory calculations constrained by 1H MAS, 27Al WURST-QCPMG, and 29Si MAS NMR experiments and FTIR measurements. Our results show that the electron-pair acceptor of AlFR Lewis sites corresponds to an AlTRI atom tricoordinated to the zeolite framework, which adsorbs a water molecule. This AlTRI-OH2 complex is reflected in 27Al NMR resonance with δiso = 70 ± 5 ppm and CQ = 13 ± 2MHz. In addition, the AlTRI atom with adsorbed acetonitrile-d3 (the probe of AlFR Lewis sites in FTIR spectroscopy) exhibits a similar 27Al NMR resonance. We suggest that these AlFR Lewis sites are formed from Al-OH-Si-O-Si-O-Si-OH-Al sequences located in 12-rings (i.e., close unpaired Al atoms).

Evidence for different behaviors of atmospheric glass alteration as a function of glass composition

The glass composition is a determining parameter that influences the glass chemical durability, particularly in atmospheric conditions (defined by the relative humidity, RH, < 100%). This is obvious in the field of the cultural heritage (CH), where some glass compositions qualified as unstable show advanced signs of degradation under atmosphere, while others seem, on the contrary, stable. This study investigates the differences between stable and unstable glass compositions regarding the phenomenology of the atmospheric glass alteration, by means of accelerated ageing of three glass replicas followed by the characterization of their alteration layers at different scales. Over the same ageing period and experimental conditions, the two glass compositions qualified as unstable develop thick hydrated layers and a thin top layer of carbonate precipitates. Their hydrated layers are depolymerized, and they remarkably retain alkalis and non-bridging oxygens in a dense network of hydrogen bonds, as demonstrated by 29Si and 1H MAS NMR. On the contrary, the stable glass composition shows a considerably thinner hydrated layer and, relatively, a higher amount of carbonates on the surface. In unstable glasses, the retention of a significant proportion of alkalis and NBOs, probably by maintaining a basic character to the hydrated layer, seems comparatively a destabilizing factor sustaining hydration by fast network hydrolysis.

Interfacial phenomena in natural nanostructured materials based on kaolinite and calcite in blends with nanosilica and neem leaf powder

To improve structural characteristics of clays and neem leaf powder (NLP)/clay composites, nanosilica was used as an addition upon mechanical treatment. This results in composites with natural nanostructured materials (NNM) possessing improved structural characteristics and bioactivity. The blends based on NNM with crystalline kaolinite alone and kaolinite/α-quartz or calcite/α-quartz + clay and amorphous admixtures and additions with nanosilica or nanosilica/NLP were treated in a knife mill. The materials were characterized using TEM, SEM, XRD, 1H MAS and 29Si CP/MAS NMR, FTIR spectroscopy, elemental analysis, nitrogen adsorption, quantum chemistry, release of bioactive components and bactericidal effects against various bacteria. There are regularities in the characteristics depending on a type of NNM, particulate morphology and textural features of solids. The morphological and structural characteristics of components slightly changed in the blends because the treatment was performed using relatively low mechanical loading. Release of chlorophyll and anthocyanins is greater for NLP/A―300/NNM composites (especially characterized by minimal confined space effects) than for NLP alone. Some clays and composites demonstrate bactericidal activity tested against four types of bacteria. The morphological, textural, and structural characteristics of the NNM/A―300 and NNM/A―300/NLP systems, as well NLP transformation into a nanostructured state, allow one to expect high activity of the composites as bioactive systems interesting for practical applications in medicine and cosmetics.

1H, 19F and 29Si MAS NMR investigations of synthetic lepidolite samples with variable OH/F ratios

¹H, ¹⁹F and ²⁹Si MAS NMR investigations of synthetic lepidolite samples with variable OH/F ratios

Nanostructured Polymethylsiloxane/Fumed Silica Blends.

Polymethylsiloxane (PMS) and fumed silica, alone and in a blended form (1:1 w/w), differently pretreated, hydrated, and treated again, were studied using TEM and SEM, nitrogen adsorption–desorption, 1H MAS and 29Si CP/MAS NMR spectroscopy, infrared spectroscopy, and methods of quantum chemistry. Analysis of the effects of adding water (0–0.5 g of water per gram of solids) to the blends while they are undergoing different mechanical treatment (stirring with weak (~1–2 kg/cm2) and strong (~20 kg/cm2) loading) show that both dry and wetted PMS (as a soft material) can be grafted onto a silica surface, even with weak mechanical loading, and enhanced mechanical loading leads to enhanced homogenization of the blends. The main evidence of this effect is strong nonadditive changes in the textural characteristics, which are 2–3 times smaller than additive those expected. All PMS/nanosilica blends, demonstrating a good distribution of nanosilica nanoparticles and their small aggregates in the polymer matrix (according to TEM and SEM images), are rather meso/microporous, with the main pore-size distribution peaks at R > 10 nm in radius and average <RV> values of 18–25 nm. The contributions of nanopores (R < 1 nm), mesopores (1 nm < R < 25 nm), and macropores (25 nm < R < 100 nm), which are of importance for studied medical sorbents and drug carriers, depend strongly on the types of the materials and treatments, as well the amounts of water added. The developed technique (based on small additions of water and controlled mechanical loading) allows one to significantly change the morphological and textural characteristics of fumed silica (hydrocompaction), PMS (drying–wetting–drying), and PMS/A-300 blends (wetting–drying under mechanical loading), which is of importance from a practical point of view.

Effects of pre-adsorbed water on methane adsorption onto blends with hydrophobic and hydrophilic nanosilicas

The effects of water pre-adsorbed onto hydro-compacted hydrophilic nanosilica A-300 and its blend with hydrophobic AM1 (dimethyldichlorosilane hydrophobized A-300) on methane adsorption depend on the amounts of water (h = 0.005−0.25 g per gram of dry solids) and the AM1/A-300 ratio (1:1, 3:1, and 5:1), as well on the pretreatment conditions. The interfacial and temperature behaviors of co-adsorbed water and methane were analyzed using low-temperature 1H NMR spectroscopy (for static samples), cryoporometry, and quantum chemistry. The structural, morphological, and textural characteristics of the materials were studied using 1H MAS and 29Si CP/MAS NMR spectroscopy, infrared spectroscopy, SEM, TEM, and nitrogen adsorption. It is unexpected that 1H NMR signal of methane increases with increasing temperature. This could be occurred due to enhanced molecular mobility and structure changes in mobile water and ice clusters bound in voids between silica nanoparticles in their aggregates, as well because of changes in the textural characteristics of the pretreated blends. The maximal adsorption of methane (38 mg/g at 285 K) is observed for AM1/A-300 (3:1) hydrated at h = 0.1 g/g. An increase or decrease in the content of hydrophobic nanosilica AM1 in the blends, as well the bound water amount, results in a decrease in the methane adsorption, but hydro-compaction of the blends results in increased methane adsorption.

Red-emitting K3HF2WO2F4:Mn4+ for application in warm-white phosphor-converted LEDs - optical properties and magnetic resonance characterization.

We report novel efficient Mn4+ phosphors of composition K3HF2MO2F4:Mn4+ (M = Mo, W) containing [HF2]- and octahedral [MO2F4]2- building units. The phosphor exhibits strong absorption at 450 nm and an external quantum yield of 90%. K3HF2WO2F4:0.01Mn4+ provides a sufficiently high quenching temperature T1/2 of about 400 K and is applicable as a converter for (In,Ga)N LEDs. The EPR spectrum is consistent with the presence of a MnF62- species at giso = 1.983. 19F MAS NMR results confirm the 2 : 1 ratio of the metal-bound fluoride species to the hydrogen difluoride group as predicted from the chemical formula. There are two distinct M-bonded species in a 1 : 1 ratio, indicating that the W and Mo octahedra are exclusively of the MO2F42- type, with the two oxygen atoms in cis-position. Their extremely sharp 19F resonances indicate a fast, near-isotropic reorientational process at room temperature that is on the millisecond timescale. For the HF2- group, the 19F and 1H MAS NMR spinning sideband profiles reveal the geometry of a linear centrosymmetric three-spin system with an H-F bond distance of 1.14 Å.

NMR and XRD Study of Hydrogen Bonding in Picolinic Acid N-Oxide in Crystalline State and Solutions: Media and Temperature Effects on Potential Energy Surface.

Solvent and temperature effects on H-bonding in crystalline picolinic acid N-oxide (PANO) and in solutions were studied by NMR (1H MAS and 1H-13C CP/MAS) and X-ray diffraction (XRD) methods. The single-crystal XRD experiments on β-polymorph were carried out at 105 and 299 K. 13C chemical shifts of PANO pyridine ring carbons were chosen as an effective diagnostic tool for the H-bond sensing. The crystal field in PANO forces the proton displacement from donor to acceptor atoms much stronger than the solvent reaction field, including that created by the most polar solvents. NMR and XRD data for crystalline PANO do not confirm any H-bond geometry changes in the studied temperature range. On the contrary, a considerable contraction of r(O-H) bond was observed for PANO in acetonitrile (ACN) solution upon heating. The relative contraction of r(O-H) bond with respect to R(O···O) perfectly fits the global dielectric scheme deduced for a vast set of common solvents and the dependence of the dielectric permittivity of ACN on temperature. The subtle H-bond changes can be explained by the temperature dependence of the shape of potential energy surface in the liquid state. Both factors, temperature and dielectric permittivity, are comparable in triggering this effect.

Chemically Modified Silica Materials as Model Systems for the Characterization of Water-Surface Interactions

Abstract A series of novel functionalized mesoporous silica-based materials with well-defined pore diameters, surface functionalization and surface morphology is synthesized by co-condensation or grafting techniques and characterized by solid-state NMR spectroscopy, DNP enhanced solid state-NMR and thermodynamic techniques. These materials are employed as host-systems for small-guest molecules like water, small alcohols, carbonic acids, small aromatic molecules, binary mixtures and others. The phase-behavior of these confined guests is studied by combinations of one dimensional solid-state NMR techniques (1H MAS, 2H-line shape analysis, 13C CPMAS) and two-dimensional correlation experiments like 1H-29Si- solid-state HETCOR.

Cation dynamics by 1H and 13C MAS NMR in hybrid organic-inorganic (CH3CH2NH3)2CuCl4.

To understand the dynamics of the cation in layered perovskite-type (CH3CH2NH3)2CuCl4, the temperature-dependent chemical shifts and spin–lattice relaxation times T1ρ in the rotating frame have been measured using 1H magic angle spinning nuclear magnetic resonance (MAS NMR) and 13C cross-polarization (CP)/MAS NMR techniques. Each proton and carbon in the (CH3CH2NH3)+ cation is distinguished in MAS NMR spectra. The Bloembergen–Purcell–Pound (BPP) curves for 1H T1ρ in CH3CH2 and NH3, and for the 13C T1ρ in CH3 and CH2 are revealed to have minima at low temperatures. This implies that the curves represent the CH3 and NH3+ rotational motions. The amplitude of the cationic motion is enhanced at the C-end, that is, the N-end of the organic cation is fixed to the inorganic layer through N–H⋯Cl hydrogen bonds, and T1ρ becomes short with larger-amplitude molecular motions.

Engineering Codrug Solid Forms: Mechanochemical Synthesis of an Indomethacin–Caffeine System

This article reports on the preparation and solid-state characterization of an indomethacin–caffeine drug–drug cocrystal (or codrug) in a 1:1 stoichiometry. These two active ingredients are frequently coadministered as part of a therapy against strong migraines, in a commercially available fixed dose combination formulation. The X-ray crystal structure of the codrug is characterized by a hydrogen bond interaction between the carboxylic moiety of indomethacin and the purinic nitrogen atom of caffeine. The combination of multinuclear and multidimensional solid-state NMR measurements (1H MAS, 13C and 15N CPMAS, 1H DQ MAS, 13C–1H HETCOR, 14N–1H J- and D-HMQC), as well as IR data, provided spectroscopic evidence about the hydrogen atom position along the hydrogen bond axis, thereby confirming the neutral nature of the cocrystal. Furthermore, dissolution kinetic tests revealed superior bioavailability of indomethacin in the codrug compared to indomethacin alone and to an indomethacin–caffeine physical mixture. ...

Mesoporous tin oxide: An efficient catalyst with versatile applications in acid and oxidation catalysis

Mesoporous tin oxide was prepared by template assisted and template-free methods. As-prepared materials were calcined at various temperatures to generate different nature (Brønsted and Lewis), amount and strength of acidic sites. The physico-chemical properties of the catalysts were studied by XRD, N2 sorption, pyridine-FTIR, NH3-TPD, DRS UV-vis, TGA, SEM, TEM, 1H MAS and 119Sn MAS NMR analyses. The catalytic behavior of mesoporous tin oxide catalysts was evaluated for acetalization and ketalization of glycerol with benzaldehyde and acetone respectively under solvent free conditions. The catalytic performance of mesoporous tin oxide was compared with that of other conventional solid acid catalysts namely H-ZSM-5, H-mordenite, H-beta, Al-MCM-41, Al-SBA-15 and Al-TUD-1. The efficiency of mesoporous tin oxide was also tested for cyclohexene epoxidation reaction. The catalyst prepared by template assisted method showed excellent catalytic performance compared to other catalysts due the difference in nature and amount of acidic sites in the catalyst. Meso-SnO2-T-350 was stable and reusable catalyst for four cycles without any appreciable loss in activity, and therefore it offers a good catalyst for potentially wide applications.

Molecular Salts of the Antidepressant Venlafaxine: An Effective Route to Solubility Properties Modifications

The possibility of decreasing the solubility of the antidepressant drug venlafaxine hydrochloride by formation of molecular salts with organic acids accepted by the Pharmacopeia has been successfully investigated. Reacting venlafaxine with coumaric, ferulic, oxalic, salicylic, fumaric, and citric acids results in the protonation of the amino group and formation of the corresponding 1:1 molecular salts. All compounds have been characterized by a combination of solid state techniques, i.e., single crystal and powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy and solid-state NMR (1H MAS, 13C and 15N CPMAS, 1H DQ MAS, two-dimensional (2D) 13C–1H HETCOR, and 2D 14N–1H J-HMQC) spectroscopy. Intrinsic dissolution tests were performed on the pure salts, and suitable candidates were selected for the preparation of solid formulations with excipients; dissolution profiles for the solid formulations were measured in water and sodium chlori...

Differentiation of the solid-state NMR signals of gel, zeolite phases and water species in geopolymer-zeolite composites

Geopolymer-zeolite composites were synthesized using a silica-rich industrial byproduct from chlorosilane production and sodium aluminate. Pastes were cured at 80°C and 80% RH, and subsequently dried in two different climates: at 23°C and 50% RH, and under vacuum. 1H MAS, 23Na MAS and 29Si MAS NMR and XRD measurements were performed after the drying procedures as well as after subsequent aging. Zeolite Na-A was found beside traces of faujasite-type zeolite and zeolite EMT as major crystalline phases in the cured composites; the fraction of geopolymeric gel in the reaction products was determined to be ~18% on a molar basis. Various water species could be distinguished using 1H MAS and 1H-29Si CP MAS NMR, applying rotor-synchronized echo experiments. The largest fraction of the pore water resides in the α-cages of the zeolite Na-A and in the geopolymeric gel; in addition, water exists in the β-cages of the zeolites and adsorbed at sodium ions. The water species in α-cages and in the pores of the geopolymeric gel exhibit slightly different chemical shifts of 4.7ppm and 4.9ppm, respectively, in the 1H MAS NMR spectra. Changes of the water content in the geopolymer pores of differently dried samples were observed and led to slightly varied chemical shifts in the 29Si MAS NMR spectra too. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability.

2H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H2ca

Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5’-dimethyl-2,2’-bipyridine (55DMBP) and chloranilic acid (H2ca), was investigated by use of 2H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N+-H …O − in the antiferroelectric phase were clearly observed as the splitting of the side band of the 2H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D 2ca. The temperature dependence of the spin-lattice relaxation time was measured of the N+-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N+-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol−1.