Exposing active sites in zeolites with fluoropyridines as NMR probe molecules.

Active sites in zeolites are crucial for catalysis, but their identification remains challenging due to structural complexity. Solid-state NMR, a key tool for studying zeolites, can struggle with directly detecting acidic properties due to the quadrupolar nature of ubiquitous metal dopants. Here, we use fluorinated pyridine as a probe to identify active sites in HY and HZSM-5, two important solid acid catalysts.

New insights into bioactive Ga(III) hydroxyquinolinate complexes from UV-vis, fluorescence and multinuclear high-field NMR studies.

There is current interest in the anticancer and antimicrobial activities of Ga(III) tris-hydroxyquinolinate complexes, and hence their solution and solid-state chemistry. Here, we have studied the formation, stability and structure of a novel tris-5,7-dibromo-8-hydroxyquinolinate Ga(III) complex [Ga(Br-HQ)]. Reactions of 5,7-dibromo-8-hydroxyquinoline with Ga(NO) in DMSO were followed using electronic absorption and emission spectroscopy, and revealed the slow but concerted coordination of three chelated ligands, with ligand deprotonation being the apparent rate-limiting step, facilitated by basic Ga(III) hydroxido species.

A fast ceramic mixed OH/H ionic conductor for low temperature fuel cells.

Low temperature ionic conducting materials such as OH and H ionic conductors are important electrolytes for electrochemical devices. Here we show the discovery of mixed OH/H conduction in ceramic materials. SrZrYO exhibits a high ionic conductivity of approximately 0.

Disorder and Oxide Ion Diffusion Mechanism in LaSrGaO Melilite from Nuclear Magnetic Resonance.

Layered tetrahedral network melilite is a promising structural family of fast ion conductors that exhibits the flexibility required to accommodate interstitial oxide anions, leading to excellent ionic transport properties at moderate temperatures. Here, we present a combined experimental and computational magic angle spinning (MAS) nuclear magnetic resonance (NMR) approach which aims at elucidating the local configurational disorder and oxide ion diffusion mechanism in a key member of this structural family possessing the LaSrGaO composition. O and Ga MAS NMR spectra display complex spectral line shapes that could be accurately predicted using a computational ensemble-based approach to model site disorder across multiple cationic and anionic sites, thereby enabling the assignment of bridging/nonbridging oxygens and the identification of distinct gallium coordination environments.

Probing fluconazole deposition inside mesoporous silica using solid-state NMR spectroscopy: Crystallization of a confined metastable form and phase transformations under storage conditions.

Encapsulation of molecules into mesoporous silica carriers continues to attract considerable interest in the area of drug delivery and crystal engineering. Here, MCM-41, SBA-15 and MCF silica matrices were used to encapsulate fluconazole (FLU), a pharmaceutically relevant molecule with known conformational flexibility, using the melting method. The composites have been characterized using H, C and F NMR spectroscopy, nitrogen adsorption, PXRD and thermal analysis (DSC, TGA).

Ectopic callose deposition into woody biomass modulates the nano-architecture of macrofibrils.

Plant biomass plays an increasingly important role in the circular bioeconomy, replacing non-renewable fossil resources. Genetic engineering of this lignocellulosic biomass could benefit biorefinery transformation chains by lowering economic and technological barriers to industrial processing. However, previous efforts have mostly targeted the major constituents of woody biomass: cellulose, hemicellulose and lignin.

Post-acquisition correction of NMR spectra distorted by dynamic and static field inhomogeneity of cryogen-free magnets.

Post-acquisition correction of NMR spectra is an important part of NMR spectroscopy that enables refined NMR spectra to be obtained, clean from undesirable out-phasing, broadening and noising. We describe analytical and numerical mathematical methods for post-acquisition correction of NMR spectra distorted by static and dynamic magnetic field inhomogeneity caused by imperfections of main superconducting coils and the cold head operation, typical for cryogen-free magnets. For the dynamic inhomogeneity, we apply a variant of the general reference deconvolution method, complemented with our mathematical analysis of spectral parameters.

Cryogen-free 400 MHz (9.4 T) solid state MAS NMR system with liquid state NMR potential.

We show that the temporal magnetic field distortion generated by the Cold Head operation can be removed and high quality Solid-State Magic Angle Spinning NMR results can be obtained with a cryogen-free magnet. The compact design of the cryogen-free magnets allows for the probe to be inserted either from the bottom (as in most NMR systems) or, more conveniently, from the top. The magnetic field settling time can be made as short as an hour after a field ramp.

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials.

We report the modulation of reactivity of nitrogen dioxide (NO ) in a charged metal-organic framework (MOF) material, MFM-305-CH in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl ions in the pores. Uptake of NO into MFM-305-CH leads to reaction between NO and Cl to give nitrosyl chloride (NOCl) and NO anions. A high dynamic uptake of 6.

Bimetallic Aluminum- and Niobium-Doped MCM-41 for Efficient Conversion of Biomass-Derived 2-Methyltetrahydrofuran to Pentadienes.

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of Al and Nb sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure.

Synthesis and structural characterisation of solid titanium(IV) phosphate materials by means of X-ray absorption and NMR spectroscopy.

Solid titanium phosphate, TiP, materials hold great promise for wastewater treatment for removal of metal ions and complexes. A series of TiP materials, synthesised at mild conditions and short reaction times, have been structurally characterised using solid-state X-ray absorption spectroscopy, phosphorus and titanium K edge XANES and EXAFS, and P and Ti NMR spectroscopy. The titanium K edge EXAFS data of α-Ti(HPO)·HO (α-TiP) revealed octahedral coordination of oxygens around titanium.

Molecular and cellular insight into Escherichia coli SslE and its role during biofilm maturation.

Escherichia coli is a Gram-negative bacterium that colonises the human intestine and virulent strains can cause severe diarrhoeal and extraintestinal diseases. The protein SslE is secreted by a range of pathogenic and commensal E. coli strains.

Solid-State Structural Properties of Alloxazine Determined from Powder XRD Data in Conjunction with DFT-D Calculations and Solid-State NMR Spectroscopy: Unraveling the Tautomeric Identity and Pathways for Tautomeric Interconversion.

We report the solid-state structural properties of alloxazine, a tricyclic ring system found in many biologically important molecules, with structure determination carried out directly from powder X-ray diffraction (XRD) data. As the crystal structures containing the alloxazine and isoalloxazine tautomers both give a high-quality fit to the powder XRD data in Rietveld refinement, other techniques are required to establish the tautomeric form in the solid state. In particular, high-resolution solid-state N NMR data support the presence of the alloxazine tautomer, based on comparison between isotropic chemical shifts in the experimental N NMR spectrum and the corresponding values calculated for the crystal structures containing the alloxazine and isoalloxazine tautomers.

A novel multinuclear solid-state NMR approach for the characterization of kidney stones.

The spectroscopic study of pathological calcifications (including kidney stones) is extremely rich and helps to improve the understanding of the physical and chemical processes associated with their formation. While Fourier transform infrared (FTIR) imaging and optical/electron microscopies are routine techniques in hospitals, there has been a dearth of solid-state NMR studies introduced into this area of medical research, probably due to the scarcity of this analytical technique in hospital facilities. This work introduces effective multinuclear and multidimensional solid-state NMR methodologies to study the complex chemical and structural properties characterizing kidney stone composition.

Drug-Polymer Interactions in Acetaminophen/Hydroxypropylmethylcellulose Acetyl Succinate Amorphous Solid Dispersions Revealed by Multidimensional Multinuclear Solid-State NMR Spectroscopy.

The bioavailability of insoluble crystalline active pharmaceutical ingredients (APIs) can be enhanced by formulation as amorphous solid dispersions (ASDs). One of the key factors of ASD stabilization is the formation of drug-polymer interactions at the molecular level. Here, we used a range of multidimensional and multinuclear nuclear magnetic resonance (NMR) experiments to identify these interactions in amorphous acetaminophen (paracetamol)/hydroxypropylmethylcellulose acetyl succinate (HPMC-AS) ASDs at various drug loadings.

Synergy of Solid-State NMR, Single-Crystal X-ray Diffraction, and Crystal Structure Prediction Methods: A Case Study of Teriflunomide (TFM).

In this work, for the first time, we present the X-ray diffraction crystal structure and spectral properties of a new, room-temperature polymorph of teriflunomide (TFM), CSD code 1969989. As revealed by DSC, the low-temperature TFM polymorph recently reported by Gunnam et al. undergoes a reversible thermal transition at -40 °C.

Cl- H Heteronuclear correlation magic-angle spinning nuclear magnetic resonance experiments for probing pharmaceutical salts.

Heteronuclear multiple-quantum coherence (HMQC) pulse sequences for establishing heteronuclear correlation in solid-state nuclear magnetic resonance (NMR) between Cl and H nuclei in chloride salts under fast (60 kHz) magic-angle spinning (MAS) and at high magnetic field (a H Larmor frequency of 850 MHz) are investigated. Specifically, recoupling of the Cl- H dipolar interaction using rotary resonance recoupling with phase inversion every rotor period or the symmetry-based SR4 pulse sequences are compared. In our implementation of the population transfer (PT) dipolar (D) HMQC experiment, the satellite transitions of the Cl nuclei are saturated with an off-resonance WURST sweep, at a low nutation frequency, over the second spinning sideband, whereby the WURST pulse must be of the same duration as the recoupling time.

Labeling and Probing the Silica Surface Using Mechanochemistry and O NMR Spectroscopy*.

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly O enrichment protocols to help to understand the structure and reactivity of materials by using O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca.

A Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives.

Ca nuclear magnetic resonance (NMR) spectroscopy has been extensively applied to the detailed study of octacalcium phosphate (OCP), Ca (HPO ) (PO ) .5H O, and hybrid derivatives involving intercalated metabolic acids (viz., citrate, succinate, formate, and adipate).

Characterization of and Structural Insight into Struvite-K, MgKPO·6HO, an Analogue of Struvite.

Struvite-K (MgKPO·6HO) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including nuclear waste management and rapid road repair. Struvite-K is also of interest in sustainable phosphate recovery from wastewater and, as such, a detailed knowledge of the crystal chemistry and high-temperature behavior is required to support further laboratory investigations and industrial applications. In this study, the local chemical environments of synthetic struvite-K were investigated using high-field solid-state Mg and K MAS NMR techniques, alongside P MAS NMR and thermal analysis.

Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials*.

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis.

Structural heterogeneities in starch hydrogels.

Hydrogels have a complex, heterogeneous structure and organisation, making them promising candidates for advanced structural and cosmetics applications. Starch is an attractive material for producing hydrogels due to its low cost and biocompatibility, but the structural dynamics of polymer chains within starch hydrogels are not well understood, limiting their development and utilisation. We employed a range of NMR methodologies (CPSP/MAS, HR-MAS, HPDEC and WPT-CP) to probe the molecular mobility and water dynamics within starch hydrogels featuring a wide range of physical properties.