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Dabrafenib (DBF), an anticancer drug, exhibits isostructural properties in its hydrate (DBFâH2O) and perhydrate (DBFâH2O2) forms, as revealed by single-crystal X-ray diffraction. Despite the H2O and H2O2 solvent molecules occupying identical locations, the two polymorphs have different thermal behaviors. In general, determination of stoichiometry of H2O in the perhydrate crystals is difficult due to the presence of both H2O and H2O2 in the same crystal voids. This study utilizes magic-angle spinning (MAS) solid-state NMR (SSNMR) combined with gauge-included projector augmented wave calculations to characterize the influence of solvent molecules on the local environment in pseudopolymorphs. SSNMR experiments were employed to assign 1H, 13C, and 15N peaks and identify spectral differences in the isostructural pseudopolymorphs. Proton spectroscopy at fast MAS was used to identify and quantify H2O2/H2O in DBFâH2O2 (mixed hydrate/perhydrate). 1H-1H dipolar-coupling-based experiments were recruited to confirm the 3D molecular packing of solvent molecules in DBFâH2O and DBFâH2O2. Homonuclear (1H-1H) and heteronuclear (1H-14N) distance measurements, in conjunction with diffraction structures and optimized hydrogen atom positions by density functional theory, helped decipher local interactions of H2O2 with DBF and their geometry in DBFâH2O2. This integrated X-ray structure, quantum chemical calculations, and NMR study of pseudopolymorphs offer a practical approach to scrutinizing crystallized solvent interactions in the crystal lattice even without high-resolution crystal structures or artificial sample enrichment.
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The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on 1H, 13C, and 14N nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm-2 current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).
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Radio-frequency (RF) field calibration is essential in NMR spectroscopy. A common practice is to collect a nutation curve by varying the pulse length in a direct single-pulse excitation experiment or in a cross-polarization magic-angle spinning with a flip-back pulse experiment. From the null points on this curve, one can calculate the RF field strength. Nevertheless, the practical implementation is not always straightforward or can even be unrealizable, especially for low-receptivity nuclei owing to their associated low sensitivity. Several researchers used an approach that involves utilizing other nuclei with more sensitivity but nearly identical Larmor frequencies to that of the nucleus of interest. However, such an approach has not been a common practice so far. In this work, we have systematically revisited this approach using 3.2 mm rotors on different sets of nuclei covering a Larmor frequency range up to 80 MHz. The effect of solid- and solution-states on RF field strength measurements has been investigated. The detection of each set of nuclei is then carried out with a resonant circuit in the NMR probe consisting of identical coils and capacitors. Our methodology is illustrated by recording 135/137Ba NMR spectra of BaTiO3 without prior 135/137Ba RF field calibration.
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Covalent organic nanotubes (CONTs) are one-dimensional porous frameworks constructed from organic building blocks via dynamic covalent chemistry. CONTs are synthesized as insoluble powder that restricts their potential applications. The judicious selection of 2,2'-bipyridine-5,5'-dicarbaldehyde and tetraaminotriptycene as building blocks for TAT-BPy CONTs has led to constructing flexible yet robust and self-standing fabric up to 3 µm thickness. The TAT-BPy CONTs and TAT-BPy CONT fabric have been characterized by solid-state one-dimensional (1D) 13C CP-MAS, two-dimensional (2D) 13C-1H correlation NMR, 2D 1H-1H DQ-SQ NMR, and 2D 14N-1H correlation NMR spectroscopy. The mechanism of fabric formation has been established by using high-resolution transmission electron microscopy and scanning electron microscopy techniques. The as-synthesized viscoelastic TAT-BPy CONT fabric exhibits high mechanical strength with a reduced modulus (Er) of 8 (±3) GPa and hardness (H) of 0.6 (±0.3) GPa. Interestingly, the viscoelastic fabric shows time-dependent elastic depth recovery up to 50-70%.
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Detecting proton and nitrogen correlations in solid-state nuclear magnetic resonance (NMR) is important for the structural determination of biological and chemical systems. Recent advances in proton detection-based approaches under fast magic-angle spinning have facilitated the detection of 1H-14N correlations by solid-state NMR. However, observing remote 1H-14N correlations by these approaches is still a challenge, especially for 14N sites having large quadrupolar couplings. To address this issue, we introduce the 1H-14N overtone continuous wave rotational-echo saturation-pulse double-resonance (1H-14N OT CW-RESPDOR) sequence. Unlike regular 2D correlation experiments where the indirect dimension is recorded in the time domain, the 1H-14N OT CW-RESPDOR experiment is directly observed in the frequency domain. A set of 1H-14N OT CW-RESPDOR filtered 1H spectra is recorded at varying 14N OT frequencies. Thanks to the selective nature of the 14N OT pulse, the filtered 1H spectra appear only if the 14N OT frequency hits the positions of the 14N OT central band or one of the spinning sidebands. This set of filtered 1H spectra represents a 2D 1H-14N OT correlation map. We have also investigated the optimizable parameters for CW-RESPDOR and figured out that these parameters are not strictly needed for our working magnetic field of 14.1 T. Hence, the experiment is easy to set up and requires almost no optimization. We have demonstrated the experimental feasibility of 1H-14N OT CW-RESPDOR on monoclinic L-histidine and L-alanyl L-alanine. The remote 1H-14N correlations have been efficiently detected, no matter how large the 14N quadrupolar interaction is, and agree with the crystal structures. In addition, based on the remote 1H-14N correlations from the non-protonated 14N site of L-histidine, we can unambiguously distinguish the orthorhombic and monoclinic forms.
Assuntos
Histidina , Prótons , Histidina/química , Imageamento por Ressonância Magnética , Espectroscopia de Ressonância Magnética/métodos , NitrogênioRESUMO
Fast magic-angle spinning (≥60 âkHz) technique has enabled the acquisition of high-resolution 1H NMR spectra of solid materials. However, the spectral interpretation is still difficult because the 1H peaks are overlapped due to the narrow chemical shift range and broad linewidths. An additional 13C or 14N or 1H dimension possibly addresses the issues of overlapped proton resonances, but it leads to the elongated experimental time. Herein, we introduce a single-channel 1H experiment to separate the overlapped 1H peak and identify its spatially proximal 1H-1H correlations. This sequence combines selective excitation, selective 1H-1H polarization transfer by selective recoupling of protons (SERP), and broadband 1H recoupling by back-to-back (BABA) recoupling sequences. The concept for 1H separation is based on (i) the selective excitation of a well-resolved 1H peak and (ii) the selective dipolar polarization transfer from this isolated 1H peak to one of the 1H peaks in the overlapped/poor resolution region by SERP and (iii) the detection of 1H-1H correlations from these two 1H peaks to other neighboring 1Hs by BABA. We demonstrated the applicability of this approach to identify overlapped peaks on two molecules, ß-L-aspartyl-l-alanine and Pioglitazone.HCl. The sequence allows the clear observation of 1H-1H correlations from an overlapped 1H peak without an additional heteronuclear dimension and ensures efficient polarization transfers that leads to twelve fold reduction in experimental time compared to 14N edited experiments. The limitation and the conditions of applicability for this approach are discussed in detail.
Assuntos
Imageamento por Ressonância Magnética , Prótons , Espectroscopia de Ressonância Magnética/métodosRESUMO
Three-dimensional electron diffraction crystallography (microED) can solve structures of sub-micrometer crystals, which are too small for single crystal X-ray crystallography. However, R factors for the microED-based structures are generally high because of dynamic scattering. That means R factor may not be reliable provided that kinetic analysis is used. Consequently, there remains ambiguity to locate hydrogens and to assign nuclei with close atomic numbers, like carbon, nitrogen, and oxygen. Herein, we employed microED and ssNMR dipolar-based experiments together with spin dynamics numerical simulations. The NMR dipolar-based experiments were 1H-14N phase-modulated rotational-echo saturation-pulse double-resonance (PM-S-RESPDOR) and 1H-1H selective recoupling of proton (SERP) experiments. The former examined the dephasing effect of a specific 1H resonance under multiple 1H-14N dipolar couplings. The latter examined the selective polarization transfer between a 1H-1H pair. The structure was solved by microED and then validated by evaluating the agreement between experimental and calculated dipolar-based NMR results. As the measurements were performed on 1H and 14N, the method can be employed for natural abundance samples. Furthermore, the whole validation procedure was conducted at 293 K unlike widely used chemical shift calculation at 0 K using the GIPAW method. This combined method was demonstrated on monoclinic l-histidine.
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Proton-detected solid-state NMR at fast Magic Angle Spinning (MAS) is becoming the norm to characterize molecules. Routinely 1H-1H and 1H-X dipolar couplings are used to characterize the structure and dynamics of molecules. Selective proton recoupling techniques are emerging as a method for structural characterization via estimation of qualitative and quantitative distances. In the present study, we demonstrate through numerical simulations and experiments that the well-characterized CNvn sequences can also be tailored for selective recoupling of proton spins by employing C elements of the type (ß)Φ(4ß)Φ+π(3ß)Φ. Herein, several CNvn sequences were examined through numerical simulations and experiments. C614 recoupling sequence with a modified POST-element ((ß)Φ(4ß)Φ+π(3ß)Φ) shows selective polarization transfer efficiencies on the order of 40-50% between various proton spin pairs in fully protonated samples at rf amplitudes ranging from 0.3 to 0.8 times the MAS frequency. These selective recoupling sequences have been labeled as frequency-selective-CNvn sequences. The extent of selectivity, polarization transfer efficiency and the feasibility of experimentally measuring proton-proton distances in fully protonated samples are explored here. The development of efficient and robust selective 1H-1H recoupling experiments is required to structurally characterize molecules without artificial isotope enrichment or the need for diffracting crystals.
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Accurate distance measurements between proton and nitrogen can provide detailed information on the structures and dynamics of various molecules. The combination of broadband phase-modulated (PM) pulse and rotational-echo saturation-pulse double-resonance (RESPDOR) sequence at fast magic-angle spinning (MAS) has enabled the measurement of multiple 1H-14N distances with high accuracy. However, complications may arise when applying this sequence to systems with multiple inequivalent 14N nuclei, especially a single 1H sitting close to multiple 14N atoms. Due to its broadband characteristics, the PM pulse saturates all 14N atoms; hence, the single 1H simultaneously experiences the RESPDOR effect from multiple 1H-14N couplings. Consequently, no reliable H-N distances are obtained. To overcome the problem, selective 14N saturation is desired, but it is difficult because 14N is an integer quadrupolar nucleus. Alternatively, 14N overtone (OT) NMR spectroscopy can be employed owing to its narrow bandwidth for selectivity. Moreover, owing to the sole presence of two energy levels (m = ± 1), the 14N OT spin dynamics behaves similarly to that of spin-1/2. This allows the interchangeability between RESPDOR and rotational-echo double-resonance (REDOR) since their principles are the same except the degree of 14N OT population transfer; saturation for the former whereas inversion for the latter. As the ideal saturation/inversion is impractical due to the slow and orientation-dependent effective nutation of 14N OT, the working condition is usually an intermediate between REDOR and RESPDOR. The degree of 14N OT population transfer can be determined from the results of protons with short distances to 14N and then can be used to obtain long-distance determination of other protons to the same 14N site. Herein, we combine the 14N OT and REDOR/RESPDOR to explore the feasibility of selective 1H-14N distance measurements. Experimental demonstrations on simple biological compounds of L-tyrosine.HCl, N-acetyl-L-alanine, and L-alanyl-L-alanine were performed at 14.1 T and MAS frequency of 62.5 kHz. The former two consist of a single 14N site, whereas the latter consists of two 14N sites. The experimental optimizations and reliable fittings by the universal curves are described. The extracted 1H-14N distances by OT-REDOR are in good agreement with those determined by PM-RESPDOR and diffraction techniques.
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Detecting proximities between nuclei is crucial for atomic-scale structure determination with nuclear magnetic resonance (NMR) spectroscopy. Different from spin-1/2 nuclei, the methodology for quadrupolar nuclei is limited for solids due to the complex spin dynamics under simultaneous magic-angle spinning (MAS) and radio-frequency irradiation. Herein, the performances of several homonuclear rotary recoupling (HORROR)-based homonuclear dipolar recoupling sequences are evaluated for 27 Al (spin-5/2). It is shown numerically and experimentally on mesoporous alumina that BR 2 2 1 outperforms the supercycled S3 sequence and its pure double-quantum (DQ) (bracketed) version, [S3 ], both in terms of DQ transfer efficiency and bandwidth. This result is surprising since the S3 sequence is among the best low-power recoupling schemes for spin-1/2. The superiority of BR 2 2 1 is thoroughly explained, and the crucial role of radio-frequency offsets during its spin dynamics is highlighted. The analytical approximation of BR 2 2 1 , derived in an offset-toggling frame, clarifies the interplay between offset and DQ efficiency, namely, the benefits of off-resonance irradiation and the trough in DQ efficiency for BR 2 2 1 when the irradiation is central between two resonances, both for spin-1/2 and half-integer-spin quadrupolar nuclei. Additionally, density matrix propagations show that the BR 2 2 1 sequence, applied to quadrupolar nuclei subject to quadrupolar interaction much larger than radio-frequency frequency field, can create single- and multiple-quantum coherences for near on-resonance irradiation. This significantly perturbs the creation of DQ coherences between central transitions of neighboring quadrupolar nuclei. This effect explains the DQ efficiency trough for near on-resonance irradiation, in the case of both cross-correlation and autocorrelation peaks. Overall, this work aids experimental acquisition of homonuclear dipolar correlation spectra of half-integer-spin quadrupolar nuclei and provides theoretical insights towards improving recoupling schemes at high magnetic field and fast MAS.
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The bicyclo[1.1.1]pentane (BCP) scaffold is useful in medicinal chemistry, and many protocols are available for synthesizing BCP derivatives from [1.1.1]propellane. Here, we report (1)â the α-cyclodextrin (α-CD) encapsulation of BCP derivatives, affording a stable, readily storable material from which BCPs can be easily and quantitatively recovered and (2)â new and simple protocols for deiodination reaction of 1,3-diiodo BCP to afford [1.1.1]propellane in protic/aprotic/polar/non-polar solvents. The combination of these methodologies enables simple, on-demand preparation of [1.1.1]propellane in various solvents under mild conditions from α-CD capsules containing 1,3-diiodo BCP.
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Selective recoupling of protons (SERP) is a method to selectively and quantitatively measure magnetic dipole-dipole interaction between protons and, in turn, the proton-proton distance in solid-state samples at fast magic-angle spinning. We present a bimodal operator-based Floquet approach to describe the numerically optimized SERP recoupling sequence. The description calculates the allowed terms in the first-order effective Hamiltonian, explains the origin of selectivity during recoupling, and shows how different terms are modulated as a function of the radio frequency amplitude and the phase of the sequence. Analytical and numerical simulations have been used to evaluate the effect of higher-order terms and offsets on the polarization transfer efficiency and quantitative distance measurement. The experimentally measured 1H-1H distances on a fully protonated thymol sample are â¼10%-15% shorter than those reported from diffraction studies. A semi-quantitative model combined with extensive numerical simulations is used to rationalize the effect of the third-spin and the role of different parameters in the experimentally observed shorter distances. Measurements at high magnetic fields improve the match between experimental and diffraction distances. The measurement of 1H-1H couplings at offsets different from the SERP-offset has also been explored. Experiments were also performed on a perdeuterated ubiquitin sample to demonstrate the feasibility of simultaneously measuring multiple quantitative distances and to evaluate the accuracy of the measured distance in the absence of multispin effects. The estimation of proton-proton distances provides a boost to structural characterization of small pharmaceuticals and biomolecules, given that the positions of protons are generally not well defined in x-ray structures.
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Dipolar recoupling sequences have been used to probe spatial proximity of nuclear spins and were traditionally designed to probe rare spins such as 13C and/or 15N nuclei. The multi-spin dipolar-coupling network of the rare spins is weak due to smaller couplings and large chemical shift dispersion. Therefore, the recoupling approaches were tailored to design offset compensated or broadband sequences. In contrast, protons have a substantially stronger dipolar-coupling network and much narrower chemical shift range. Broadband recoupling sequences such as radio-frequency driven recoupling (RFDR), back-to-back (BABA), and lab frame proton-proton spin diffusion have been routinely used to characterize the structures of protein/macromolecules and small molecules. Recently selective 1H-1H recoupling sequences have been proposed that combine chemical shift offset of the resolved proton spectrum (at fast MAS) with first- and second-order dipolar recoupling Hamiltonians to obtain quantitative and qualitative proton distances, respectively. Herein, we evaluate the performances of broadband and selective proton recoupling sequences such as finite pulse RFDR (fp-RFDR), band-selective spectral spin diffusion (BASS-SD), second-order cross-polarization (SOCP), and selective recoupling of proton (SERP) in terms of the selectivity and efficiency of 1H-1H polarization transfers in a dense network of proton spins and explore the possibility of measuring 1H-1H distances. We use theoretical considerations, numerical simulations, and experiments to support the distinct advantages and disadvantages of each recoupling sequence. Experiments were performed on L-histidine.HCl.H2O at a MAS frequency of 71.43 kHz. This study rationalizes the proper selection of 1H-1H recoupling sequences when working with fully protonated solids.
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Control of the reactivity of hydride (H-) in crystal structures has been a challenge because of its strong electron-donating ability and reactivity with protic species. For metal borohydrides, the dehydrogenation activity and air stability are in a trade-off, and control of the reactivity of BH4 - has been demanded. For this purpose, we synthesize a series of BH4 --based coordination polymers/metal-organic frameworks. The reactivity of BH4 - in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH4)2(dipyridylpropane)] exhibits both high dehydrogenation reactivity (1.4 wt% at 179 °C) and high air stability (50 RH% at 25 °C, 7 days). Single crystal X-ray diffraction analysis reveals that H δ+···H δ- dihydrogen interactions and close packing of hydrophobic ligands are the key for the reactivity and stability. The dehydrogenation mechanism is investigated by temperature-programmed desorption, in situ synchrotron PXRD and solid-state NMR.
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The combination of a phase-modulated (PM) saturation pulse and symmetry-based dipolar recoupling into a rotational-echo saturation-pulse double-resonance (RESPDOR) sequence has been employed to measure 1H-14N distances. Such a measurement is challenging owing to the quadrupolar interaction of 14N nucleus and the intense 1H-1H homonuclear dipolar interactions. Thanks to the recent advances in probe technology, the homonuclear dipolar interaction can be sufficiently suppressed at a fast MAS frequency (νRâ¯≥â¯60â¯kHz). PM pulse is robust to large variations of parameters on quadrupolar spins, but it has not been demonstrated under very fast MAS conditions. On the other hand, the RESPDOR sequence is applicable to such condition when it employs symmetry-based pulses during the recoupling period, but a prior knowledge on the system is required. In this article, we demonstrated the PM-RESPDOR combination for providing accurate 1H-14N distances at a very fast MAS frequency of 70â¯kHz on two samples, namely L-tyrosineâ HCl and N-acetyl-L-alanine. This sequence, supported by simulations and experiments, has shown its feasibility at νRâ¯=â¯70â¯kHz as well as the robustness to the 14N quadrupolar interaction. It is applicable to a wide range of 1H-14N dipolar coupling constants when a radio frequency field on the 14N channel is approximately 80â¯kHz or more, while the PM pulse length lasts 10 rotor periods. For the first time, multiple 1H-14N heteronuclear dipolar couplings, thus multiple quantitative distances, are simultaneously and reliably extracted by fitting the experimental fraction curves with the analytical expression. The size of the 1H-14N dipolar interaction is solely used as a fitting parameter. These determined distances are in excellent agreement with those derived from diffraction techniques.
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Porous coordination polymers (PCPs) were synthesized by using CO2 and metal borohydrides as precursors. Borohydrides converted CO2 into bridging ligands such as formate (HCO2-) or formylhydroborate ([BH(OCHO)3]-) which are available to construct porous architectures; one of them shows 380 m2 g-1 surface area.
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Proton nuclear magnetic resonance (NMR) in solid state has gained significant attention in recent years due to the remarkable resolution and sensitivity enhancement afforded by ultrafast magic-angle-spinning (MAS). In spite of the substantial suppression of 1H-1H dipolar couplings, the proton spectral resolution is still poor compared to that of 13C or 15N NMR, rendering it challenging for the structural and conformational analysis of complex chemicals or biological solids. Herein, by utilizing the benefits of double-quantum (DQ) and triple-quantum (TQ) coherences, we propose a 3D single-channel pulse sequence that correlates proton triple-quantum/double-quantum/single-quantum (TQ/DQ/SQ) chemical shifts. In addition to the two-spin proximity information, this 3D TQ/DQ/SQ pulse sequence enables more reliable extraction of three-spin proximity information compared to the regular 2D TQ/SQ correlation experiment, which could aid in revealing the proton network in solids. Furthermore, the TQ/DQ slice taken at a specific SQ chemical shift only reveals the local correlations to the corresponding SQ chemical shift, and thus it enables accurate assignments of the proton peaks along the TQ and DQ dimensions and simplifies the interpretation of proton spectra especially for dense proton networks. The high performance of this 3D pulse sequence is well demonstrated on small compounds, L-alanine and a tripeptide, N-formyl-L-methionyl-L-leucyl-L-phenylalanine (MLF). We expect that this new methodology can inspire the development of multidimensional solid-state NMR pulse sequences using the merits of TQ and DQ coherences and enable high-throughput investigations of complex solids using abundant protons.
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We demonstrate the possibility to use UDEFT (Uniform Driven Equilibrium Fourier Transform) technique in order to improve the sensitivity and the quantification of one-dimensional 29Si NMR experiments under magic-angle spinning (MAS). We derive an analytical expression of the signal-to-noise ratios of UDEFT and single-pulse (SP) experiments subsuming the contributions of transient and steady-state regimes. Using numerical spin dynamics simulations and experiments on 29Si-enriched amorphous silica and borosilicate glass, we show that 59180298059180 refocusing composite π-pulse and the adiabatic inversion using tanh/tan modulation improve the robustness of UDEFT technique to rf-inhomogeneity, offset, and chemical shift anisotropy. These pulses combined with a two-step phase cycle limit the pulse imperfections and the artifacts produced by stimulated echoes. The sensitivity of SP, UDEFT and CPMG (Carr-Purcell-Meiboom-Gill) techniques are experimentally compared on functionalized and non-functionalized mesoporous silica. Furthermore, experiments on a flame retardant material prove that UDEFT technique provides a better quantification of 29Si sites with higher sensitivity than SP method.
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The phase purity of a series of ZnAl4(OH)12SO4· nH2O layered double hydroxides (ZnAl4-LDH) obtained from a reaction of bayerite (Al(OH)3) with an excess of zinc(II) sulfate under hydrothermal conditions was investigated as a function of the reaction temperature, the duration of the hydrothermal treatment, and the zinc(II) concentration. The product quality, i.e., crystalline impurities, Al impurities, and bulk Zn:Al ratio, were assessed by powder X-ray diffraction (PXRD), 27Al MAS NMR, and elemental analysis. Structural characterization of a stoichiometric ZnAl4-LDH (120 °C, 9 days, and 2.8 M Zn(II)) showed a well-defined structure of the metal ion layer as evidenced by a single, well-defined Zn environment: i.e., no Zn substitution on the Al sites according to Zn k-edge EXAFS and PXRD. Furthermore, nearly all of the 12 different 1H atoms in the -OH groups and 4 27Al resonances could be assigned using 1H,27Al NMR correlation experiments recorded with ultrafast MAS. The interlayer water content is variable on the basis of thermogravimetric analysis and changes in the 1H MAS NMR spectra with temperature. A composition of ZnAl4(OH)12(SO4)·2.6H2O was obtained from a combination of these techniques and confirmed that ZnAl4-LDH is isostructural with the mineral nickelalumite (NiAl4(OH)12SO4·3H2O).
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Crystal melting and glass formation of coordination polymers (CPs) and metal-organic frameworks (MOFs) are rare thermal events. To expand the library of melting CP/MOFs, we utilized anti-crystal engineering in ionic liquids to construct CPs. A combination of Cu+ and 4,4'-bipyridin-1-ium derivatives afforded four melting CPs showing stable liquid and glassy states.