Angle Spinning Nuclear Magnetic Resonance Research Articles

A New Class of Oxyhalide Solid Electrolytes NaNbCl6‐2xOx for Solid‐state Sodium Batteries

AbstractSodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl6‐2xOx with a facile mechanochemical synthesis. The oxyhalide NaNbCl4O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10−4 S cm−1) compared to the halide counterpart NaNbCl6 (3×10−6 S cm−1). Structural motifs unique to the oxygen content in NaNbCl6‐2xOx are identified with 23Na and 93Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl4O electrolyte and the cobalt‐ and nickel‐free layered Na0.70Fe0.3Mn0.65Al0.05O2 cathode exhibit a maximum discharge capacity of 155 mAh g−1 with good cycle life at ambient temperature.

Dipolar Recoupling in Rotating Solids.

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) has evolved significantly over the past three decades and established itself as a vital tool for the structural analysis of biological macromolecules and materials. This review delves into the development and application of dipolar recoupling techniques in MAS NMR, which are crucial for obtaining detailed structural and dynamic information. We discuss a variety of homonuclear and heteronuclear recoupling methods which are essential for measuring spatial restraints and explain in detail the spin dynamics that these sequences generate. We also explore recent developments in high spinning frequency MAS, proton detection, and dynamic nuclear polarization, underscoring their importance in advancing biomolecular NMR. Our aim is to provide a comprehensive account of contemporary dipolar recoupling methods, their principles, and their application to structural biology and materials, highlighting significant contributions to the field and emerging techniques that enhance resolution and sensitivity in MAS NMR spectroscopy.

Study on Reaction Behavior and Phase Transformation Regularity of Montmorillonite in High-Calcium Sodium Aluminate Solution System

The diaspore is a typical representative of bauxite resources in China, which is the primary raw material for the Bayer process in alumina production, particularly in regions such as Shanxi, Guangxi, Guizhou, and Henan. Clarifying the phase transformations and reaction mechanisms of the silicon-containing minerals during the Bayer leaching process of diaspore is essential for improving the efficiency of alumina production. This article focuses on montmorillonite, which is one of the silicon-containing minerals of diaspore-type bauxite, investigating the reaction mechanisms and phase changes of montmorillonite under the high-calcium sodium aluminate solution system by using X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Magic Angle Spinning Nuclear Magnetic Resonance (MAS–NMR) and Fourier Transform Infrared Spectroscopy (FTIR). The results show that montmorillonite dissolved and transformed into Na6(AlSiO4)6 (hydrated sodium aluminosilicate) under the high-calcium sodium aluminate solution system, and calcium oxide and sodium aluminate in the solution reacted to form (CaO)3Al2O3(H2O)6 (hydrated calcium aluminate). With the increase of reaction temperature, caustic alkali concentration (Nk), and reaction time, hydrated calcium aluminate and hydrated sodium aluminosilicate react and transform into Ca3Al2SiO4(OH)8 (hydrogarnet). Under the optimal reaction conditions of a 120 min reaction time, a temperature of 240 °C, an Nk of 240 g/L, and a CaO–to–SiO2 mass ratio (C/S) of 3.5:1, the montmorillonite reaction degree can reach a maximum of 93.71%.

Study on Quality and Starch Characteristics of Powdery and Crispy Lotus Roots.

Nine varieties of lotus root (Suining, Xinhe, Zaohua, Zhonghua, L0014, L0013, Cuiyu, L0011, and Zhenzhu) were selected as the research materials to compare their differences in physical, chemical, and starch characteristics before and after boiling, frying, and microwaving. The results showed that Zhenzhu, Xinhe, L0013, Cuiyu, and Zhonghua belong to the crispy lotus root type, while L0011, L0014, Zaohua, and Suining belong to the powdery lotus root type. Furthermore, the nine varieties were characterized for their starch by optical micrograph (OM), polarized micrograph (PM), scanning electron micrograph (SEM), attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), carbon-13 cross-polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR), and differential scanning calorimetry (DSC). The starch granule of powdery lotus root appeared to be larger than that of crispy lotus, and ATR-FTIR studies revealed that the outer layer of starch granules from nine different varieties of lotus root had a highly organized structure. Moreover, XRD and 13C CP/MAS NMR analyses revealed that starch from eight lotus varieties (Suining, Xinhe, Zaohua, Zhonghua, L0014, L0013, Cuiyu, L0011) belong to the A-crystal type, while starch from Zhenzhu belongs to the CA-crystal type. The starch from powdery lotus root exhibited higher crystallinity, as well as increased gelatinization temperature and enthalpy, indicating that its crystal structure was relatively superior compared to that of crispy lotus starch. The short-range order degree, crystallinity, gelatinization temperature, and heat enthalpy of lotus starch decreased after boiling and frying but increased to varying extents after microwaving. Additionally, the heat resistance and stability of starch particles from crispy lotus root were improved after microwave treatment.

ZnH2P4N8: Case Study on Topochemical Imidonitridophosphate High-Pressure Synthesis.

Nitridophosphates are subject of current research, as they have a broad spectrum of properties and potential applications, such as ion conductors or luminescent materials. Yet, the subclass of imidonitridophosphates has been studied less extensively. The primary reason is that the controlled N-H functionalization of nitridophosphates is not straight forward, making targeted synthesis more challenging. Inspired by the high-pressure (HP) post-synthetic modification of nitridophosphates, we present the topochemical HP deprotonation of phosphorus nitride imides using the high-pressure polymorph β-PN(NH) as an example. Additional incorporation of Zn2+ results in the first quaternary transition metal imidonitridophosphate ZnH2P4N8. The crystal structure was elucidated by single-crystal X-ray diffraction (SCXRD), energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD) and solid-state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). In addition, the presence of H as part of an imide group was confirmed by IR spectroscopy. The potential of this defunctionalization approach for controlling the N-H content is demonstrated by the preparation of partially deprotonated intermediates ZnxH4-2xP4N8 (x≈0.5, 0.85). This topochemical high-pressure reaction represents a promising way to prepare, control and manipulate new imide-based materials without altering their overall anionic framework.

Catalytic benzylation of arenes using metal-ion modified HY zeolites for sustainable synthesis

Microporous zeolites are commonly employed as catalysts for the benzylation of arenes and benzyl alcohol. However, their catalytic efficiency is often compromised by diffusion limitations, particularly in reactions involving larger arenes. In this study, we developed metal-ion modified HY zeolites using Zn, Mg, and Ni as dopants and investigated their catalytic performance in the benzylation of a range of arenes, including toluene, benzene, mesitylene, p-xylene and with benzyl alcohol (BzOH). The structural and acidic properties of the modified HY zeolites were characterized using a combination of techniques including scanning electron microscopy (SEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms, Fourier-transform infrared (FTIR) spectroscopy, ammonia temperature-programmed desorption (NH₃-TPD), and proton magic angle spinning nuclear magnetic resonance (1H MAS NMR) spectroscopy. The presence of catalytically active Brønsted acid sites (BAS) was detected by 1H MAS NMR spectroscopy and it was demonstrated that the HY zeolite's acidity is considerably modulated by the addition of metal ions. The catalytic evaluations indicated that the metal-ion modified HY zeolites exhibited superior activity compared to unmodified HY zeolite, with the catalytic performance following the order Zn/HY > Ni/HY > Mg/HY > HY for the benzylation of benzyl alcohol with mesitylene. Further investigation into the mechanism revealed that the synergistic effect of metal ions and acidity plays a crucial role in enhancing the accessibility of arenes to the surface catalytic sites and thereby improving catalytic performance. These findings underscore the importance of the metal-acidity synergy in optimizing the catalytic efficacy of modified HY zeolites for selective benzylation reactions.

Ni phosphide catalysts on Al2O3‐zeolite prepared by phosphidation for methyl palmitate hydroconversion

AbstractBACKGROUNDOne‐stage hydroconversion of fatty‐acid based feedstocks is a promising way to obtain high‐quality fuels. This process is based on hydrodeoxygenation, isomerization and hydrocracking reactions. In this work, Ni2P/Al2O3‐zeolite catalysts were synthesized and tested in hydroconversion of a model compound – methyl palmitate.RESULTSNi2P catalysts were prepared by in situ phosphidation of metallic Ni/Al2O3‐zeolite precursors by PPh3. Mixtures of zeolite (30 wt%) and boehmite were peptized and extruded to obtain the support granules. SAPO‐11, ZSM‐5, ZSM‐22, ZSM‐23 and ZSM‐12 were used as a zeolite component. The catalysts and supports were characterized by a range of physicochemical methods: chemical analysis (ICP‐AES), low‐temperature N2 adsorption, H2‐temperature programmed reduction, NH3‐temperature programmed desorption, Fourier transform infrared spectroscopy of adsorbed CO, X‐ray diffraction, transmission electron microscopy, X‐ray photoelectron spectroscopy, and 27Al and 31P magic angle spinning nuclear magnetic resonance. The catalysts were studied in methyl palmitate hydroconversion (one‐stage hydrodeoxygenation‐isomerization‐hydrocracking) in a continuous‐flow fixed bed reactor at 290–340 °C, 2 MPa, H2/feed = 600 Ncm3/cm3 and LHSV = 5.3 h−1. SAPO‐11 containing sample showed high selectivity to C15 and C16 iso‐alkanes (63%, at 340 °C), and all ZSM‐containing samples showed high selectivity to cracked C5–C9 products (55–100%, at 340 °C) with varying amounts of iso‐alkanes (31–57%, at 340 °C).CONCLUSIONThe results show that by choosing the zeolite component of the catalyst it is possible to finely tune product quality in the range from low‐temperature diesel fuel to jet fuel or gasoline. © 2024 Society of Chemical Industry (SCI).

Wide-pore fully porous mixed-mode octyl/pyridyl-bonded silica material with pH-dependent surface charge reversal for high-performance hydrophobic charge-induction chromatography of proteins

In an attempt to overcome silanophilic interactions like observed on popular reversed-phase butyl‑bonded silica stationary phases in protein HPLC, a mixed-mode stationary phase based on wide pore silica (3 µm, 300 Å) was prepared by co-immobilization of octyl and 2-pyridylethyl ligands. The surface modification was performed by a new approach using synthesized functional silatranes of the above ligands and prewetted silica. It allowed to generate a dense polymeric siloxane layer on the silica surface. Butyl-bonded silica and octyl/3-aminopropyl-bonded mixed-mode silica phases were prepared for comparison. The modified silicas were subsequently characterized by elemental analysis regarding ligand densities, by solid-state 29Si and 13C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy for confirming the surface-bonded structure, and by pH-dependent ζ-potential measurements via electrophoretic light scattering providing net surface charge information at distinct pH values. While the classical butyl‑bonded stationary phase revealed negative ζ-potential over the entire pH range investigated (pH 3.5–9.5) due to residual silanols and the mixed-mode octyl/3-aminopropyl-bonded silica positive ζ-potential over the entire pH range, pH-dependent charge reversal was observed at approximately pH 5.5 for the octyl/pyridyl-bonded stationary phase. Then, a test set of proteins differing in hydrophobicities and isoelectric points was employed to evaluate the retention characteristics of all three synthesized stationary phases over the pH range of 3 to 7.5 by acetonitrile-gradient elution reversed-phase HPLC. Under acidic conditions (pH 3) the mixed-mode phases octyl/pyridyl-silica and octyl/aminopropyl-silica showed reduced retention and improved peak shapes due to repulsive interactions preventing silanophilic interactions, while protein separations by their hydrophobicities were achieved (repulsive charge-assisted protein RPLC). Finally, the prepared novel mixed-mode octyl/pyridyl-bonded stationary phase was evaluated in hydrophobic charge induction chromatography mode for protein separation of the same test set. Instead of an organic modifier gradient, elution was enforced by a pH gradient from almost neutral to acidic pH at constant organic modifier content of 10 %. This chromatographic mode showed orthogonal retention characteristics and reversed elution order compared to above organic gradient RP-HPLC. In addition, significantly less organic solvent was used under these conditions, classifying it as a green protein LC technology.

Improving the Stability of 75Li2S·25P2S5 Glass-Ceramic Electrolytes Against Lithium Metals Through Li2O Doping

The chemical and electrochemical stability between solid-state electrolytes (SSEs) and lithium metals is one of the crucial factors in the performance of all-solid-state lithium batteries (ASSLBs). Doping modification has been shown to improve the ionic conductivity and air stability of SSEs, but further research is needed to demonstrate its effectiveness in enhancing stability with lithium metal. In this work, a series of Li2O-doped 75Li2S·25P2S5 glass-ceramic electrolytes have been successfully synthesized using ball milling method. Powder X-ray diffraction (pXRD) and 7Li magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy results revealed that Li2O doping effectively reduced the percentage of residual Li2S in the ball milling stage and generated a high ionic conductivity phase Li7P3S11 during annealing. The electrolyte has the highest ionic conductivity (1.5 × 10−4 S cm−1 at room temperature) when doped with 1 mol% Li2O. Various electrochemical characterizations have shown that all doped electrolytes can effectively slow/suppress lithium dendrite formation while being chemically and electrochemically stable to some extent. Among these, 1 mol% Li2O-doped electrolyte performs the best, as the Li|1Li2O|Li cell maintains voltage and resistance nearly unchanged after 1000 h and 900 cycles, with no noticeable degradation in the material structure.

Deep purification of perfluorinated electronic specialty gas with a scalable metal–organic framework featuring tailored positive potential traps

The sequestration of trace hexafluoropropylene (C3F6) is a critical yet formidable task in the production of high-purity perfluoropropane (C3F8), an important perfluorinated electronic specialty gas (F-gas) in the advanced electronics industry. Traditional adsorbents struggle with uneven, low-pressure uptake and compromises in selectivity. This work utilizes aperture size-electrostatic potential matching within a robust metal–organic framework (Al-PMA) to facilitate selective, reversible binding of C3F6 while excluding larger C3F8 molecules. The presence of bridging hydroxyl groups (μ2-OH) in Al-PMA creates positive electrostatic potential traps that securely anchor C3F6 through strong hydrogen bonding, evidenced by in-situ infrared and 19F magic angle spinning nuclear magnetic resonance spectroscopy. Breakthrough experiments demonstrate the efficient removal of trace C3F6 from C3F8 under ambient conditions, achieving C3F8 purity exceeding 99.999%. The scalability of Al-PMA synthesis, remarkable stability, and exceptional performance highlight its potential as a promising adsorbent for industrial C3F6/C3F8 separations.

Effect of lithium concentration on the network connectivity of nuclear waste glasses

Structure of borosilicate glasses with varying Li2O contents were investigated using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR), employing 6Li, 11B, 23Na, 27Al and 29Si nuclei. 11B MAS NMR revealed that increasing Li2O contents result in formation of [BO4]− sites at the expense of BO3. 11B{6Li} and 27Al{6Li} dipolar heteronuclear multiple quantum correlation (D-HMQC) NMR revealed Li as a charge compensator for anionic tetrahedral sites with increased Li. 11B{6Li} J-coupling mediated HMQC NMR suggested the possible association of Li with non-bridging oxygens on Q2 and Q3 sites, indicating its dual role in the glass network. 29Si and 23Na MAS NMR spectra showed depolymerisation of the silicate network and shortening of Na-O bond lengths with increased Li. NMR results are supported by Raman spectroscopy and thermal analysis that indicate depolymerisation of the silicate network and a reduction in glass transition temperature at higher Li content.

A New Class of Oxyhalide Solid Electrolytes NaNbCl6-2xOx for Solid-state Sodium Batteries.

Sodium-based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid-state sodium batteries can also provide further safety advantages. However, sodium-based solid-state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium-based oxyhalide electrolytes NaNbCl6-2xOx with a facile mechanochemical synthesis. The oxyhalide NaNbCl4O exhibits close to two orders of magnitude higher ambient-temperature sodium-ion conductivity (1.03 x 10-4 S cm-1) compared to the halide counterpart NaNbCl6 (3 x 10-6 S cm-1). Structural motifs unique to the oxygen content in NaNbCl6-2xOx are identified with 23Na and 93Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x-ray diffraction (XRD). Solid-state sodium batteries assembled with NaNbCl4O electrolyte and the cobalt- and nickel-free layered Na0.70Fe0.3Mn0.65Al0.05O2 cathode exhibit a maximum discharge capacity of 155 mA h g-1 with good cycle life at ambient temperature.

Integrating HRMAS-NMR Data and Machine Learning-Assisted Profiling of Metabolite Fluxes to Classify Low- and High-Grade Gliomas.

Diagnosing and classifying central nervous system tumors such as gliomas or glioblastomas pose a significant challenge due to their aggressive and infiltrative nature. However, recent advancements in metabolomics and magnetic resonance spectroscopy (MRS) offer promising avenues for differentiating tumor grades both in vivo and ex vivo. This study aimed to explore tissue-based metabolic signatures to classify/distinguish between low- and high-grade gliomas. Forty-six histologically confirmed, intact solid tumor samples from glioma patients were analyzed using high-resolution magic angle spinning nuclear magnetic resonance (HRMAS-NMR) spectroscopy. By integrating machine learning (ML) algorithms, spectral regions with the most discriminative potential were identified. Validation was performed through univariate and multivariate statistical analyses, along with HRMAS-NMR analyses of 46 paired plasma samples. Amongst the various ML models applied, the logistics regression identified 46 spectral regions capable of sub-classifying gliomas with accuracy 87% (F1-measure 0.87, Precision 0.82, Recall 0.93), whereas the extra-tree classifier identified three spectral regions with predictive accuracy of 91% (F1-measure 0.91, Precision 0.85, Recall 0.97). Wilcoxon test presented 51 spectral regions significantly differentiating low- and high-grade glioma groups (p < 0.05). Based on sensitivity and area under the curve values, 40 spectral regions corresponding to 18 metabolites were considered as potential biomarkers for tissue-based glioma classification and amongst these N-acetyl aspartate, glutamate, and glutamine emerged as the most important markers. These markers were validated in paired plasma samples, and their absolute concentrations were computed. Our results demonstrate that the metabolic markers identified through the HRMAS-NMR-ML analysis framework, and their associated metabolic networks, hold promise for targeted treatment planning and clinical interventions in the future.

Atomic scale investigation and cytocompatibility of copper and zinc-loaded phosphate-based glasses prepared by coacervation

Phosphate-based glasses (PBGs) are bioresorbable materials that find application in the field of controlled drug delivery and tissue engineering. The structural arrangements of the phosphate units in PBGs, along with the knowledge of how therapeutic metallic ions are embedded in the phosphate network are important in understanding the degradation and targeted release properties of these materials. Using a combination of Raman spectroscopy, high-energy X-ray diffraction and 31P and 23Na solid-state magic angle spinning nuclear magnetic resonance, the atomic structure of coacervate PBGs in the system P2O5-CaO-Na2O-MOx (M = Cu or Zn) with loadings of 2, 10 and 15 mol % of M2+ have been studied as functions of composition and calcination temperature. After drying at room temperature, the structures of the phosphate network in PBG-Cu and PBG-Zn are quite similar, with that of PBG-Zn exhibiting slightly higher connectivity. Heating at 300 °C causes degradation of the polyphosphate chains, even though Q2 species remain predominant. X-ray photoelectron spectroscopy demonstrates that Cu in calcined PBGs is present in both oxidation states +1 and +2, with a predominance of the +2 state. Cu and Zn ion release data after 24 h exposure of PBGs in deionized water and cell medium DMEM show that release is proportional to their loadings. Cytotoxicity MTT assays of dissolution products of PBG-Cu/ZnX calcined at 300 °C on human osteosarcoma cells (MG-63) and on human skin cells (HaCaTs) showed good cellular response for all compositions, indicating that PBGs have great potential for both hard and soft tissue regeneration.

Resolving intermediates during the growth of aluminum deuteroxide (Hydroxide) polymorphs in high chemical potential solutions

Aluminum hydroxide polymorphs are of widespread importance yet their kinetics of nucleation and growth remain beyond the reach of current models. Here we attempt to unveil the reaction processes underlying the polymorphs formation at high chemical potential. We examine their formation in-situ from supersaturated alkaline sodium aluminate solutions using deuteration and time-resolved neutron pair distribution function analyses, which indicate the formation of individual Al(OD)3 layers as an intermediate particle phase. These layers ultimately stack to form gibbsite- or bayerite-like layered heterostructures. Ex-situ characterization of the recovered precipitates using 27Al magic angle spinning nuclear magnetic resonance spectroscopy, Raman, X-ray diffraction, and scanning electron microscopy, suggests the presence of additional intermediate states, an amorphous compound bearing both tetrahededrally- and penta-coordinated Al3+. These observations reveal the complex pathways to form Al(OD)3 monolayers via either transient pentacoordinate species or amorphous-to-ordered transitions. The subsequent crystallization of admixed gibbsite/bayerite is followed by an Al(OD)3 monolayer attachment process.

Interaction between peptide and solid lignin suggest mechanisms of abiotic covalent bond formation

The mechanisms behind the formation of soil organic matter (SOM) and associated nitrogen immobilization remain partially elusive, while ongoing research continues to shed light on carbon and nitrogen sequestration in the environment. Studies show that quinone-like structures within alkali-soluble humic extracts of SOM can bond covalently with nitrogen-containing molecules derived from proteinaceous organic matter. However, direct molecular evidence for this chemical bonding with lignin in the solid form and non-solvent-extracted SOM is lacking. Using gel-state 1H-15N heteronuclear single quantum coherence (HSQC) high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR) spectroscopy, we demonstrate that a 15N-labeled peptide (glycine-glycine-glycine-arginine, GGGR), can covalently bind to solid, untreated, brown rotted wood as well as 1,2-naphthoquinone, a quinone-model molecule typically found in degraded lignin. The new peaks in both reactions represent a change in the environment surrounding the N-functional groups. Interaction of the 15N-labeled peptide with the model quinone produced NMR cross peaks that are similar to those of the solid lignin. This suggests that the quinone-like structures are the most likely functional groups to form covalent bonds with peptides in the degraded lignin. Both Michael addition and Schiff base formation is proposed when the peptide GGGR interacts with white oak lignin and 1,2-naphthoquinone. These processes are of considerable importance to N incorporation into SOM and offer insights into how proteinaceous molecules could potentially be preserved and sequestered through covalent bond formation.

High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy of Paired Clinical Liver Tissue Samples from Hepatocellular Cancer and Surrounding Region.

The global burden of liver cancer is increasing. Timely diagnosis is important for optimising the limited available treatment options. Understanding the metabolic consequences of hepatocellular carcinoma (HCC) may lead to more effective treatment options. We aimed to document metabolite differences between HCC and matched surrounding tissues of varying aetiology, obtained at the time of liver resection, and to interpret metabolite changes with clinical findings. High-resolution magic angle spinning nuclear magnetic resonance (HRMAS-NMR) spectroscopy analyses of N = 10 paired HCC and surrounding non-tumour liver tissue samples were undertaken. There were marked HRMAS-NMR differences in lipid levels in HCC tissue compared to matched surrounding tissue and more subtle changes in low-molecular-weight metabolites, particularly when adjusting for patient-specific variability. Differences in lipid-CH3, lipid-CH2, formate, and acetate levels were of particular interest. The obvious differences in lipid content highlight the intricate interplay between metabolic adaptations and cancer cell survival in the complex microenvironment of liver cancer. Differences in formate and acetate might relate to bacterial metabolites. Therefore, documentation of metabolites in HCC tissue according to histology findings in patients is of interest for personalised medicine approaches and for tailoring targeted treatment strategies.

Synthesis methodology of pure N–A–S–H gels with wide range of Si/Al ratios at ambient temperature

AbstractThis study presents the development of a synthesis route for sodium aluminosilicate hydrate (N–A–S–H) gels with various Si/Al ratios carried out at ambient temperature. The synthesis is based on a simple “sol–gel” method, where commercial reactants are used to provide highly reactive Si and Al sources. Comprehensive characterization, including scanning electron microscope‐energy‐dispersive spectroscopy (SEM‐EDS), gas pycnometry, inductively coupled plasma (ICP), X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and magic angle spinning (MAS) nuclear magnetic resonance (NMR) (27Al, 23Na, 29Si, and 1H), is employed to verify the morphology, density, chemical composition, long‐range order, and local structure of the gels. Our results show that the synthesized gels are pure, amorphous, and homogeneous with Si/Al final ratio ranging from 1.22 to 2.23. Structural analysis of the gels indicates the synthesis of compounds with high degree of geopolymerization, which are representative of N–A–S–H gel formed in sodium‐based geopolymers.

A sol-gel templating route for the synthesis of hierarchical porous calcium phosphate glasses containing zinc

Hierarchical porous phosphate-based glasses (PPG) have great potential in biomedicine. Micropores (pore size <2 nm) increase the surface area, mesopores (pore size 2–50 nm) facilitate the absorption and diffusion of therapeutic ions and molecules making them ideal controlled delivery systems, while macropores (pore size >50 nm) facilitate the movement and diffusion of cells and fluids. In addition, the bioresorbability of PPG allows for their complete solubility in body fluid, alongside simultaneous formation of new tissue. Making PPG via the traditional melt-quenching (MQ) synthesis method used for phosphate-based glasses (PG), is not straightforward. Hence, we present here a route for preparing such glasses using a combination of sol-gel (SG) and templating methods. Hierarchical PPG in the P2O5–CaO–Na2O system with the addition of 1, 3 and 5 mol % of Zn2+ were prepared with pore dimensions ranging from the micro-to the macro scales using Pluronic 123 (P123) as a surfactant. The presence of micropores (0.30–0.46 nm), mesopores (1.75–9.35nm) and macropores (163–207 nm) was assessed via synchrotron-based Small-Angle X-ray Scattering (SAXS), with the presence of the latter two confirmed by Scanning Electron Microscopy (SEM). Structural characterisation performed using 31P solid state magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier Transform Infrared (FTIR) spectroscopies shows the presence of Q2, Q1 and Q0 phosphate species with a predominance of Q1 species in all compositions. Dissolution studies in deionised (DI) water confirm that controlled release of phosphates, Ca2+, Na+ and Zn2+ is achieved over a period of 7 days. In particular, the release of Zn2+ is proportional to its loading, making its delivery particularly easy to control.

Fabrication of polydopamine-modified cellulose hydrogel for controlled release of α-mangostin.

Hydrogels are notable for their outstanding absorbent qualities, satisfactory compatibility with biological systems, ability to degrade, and inherent safety, all of which contribute to their high demand in the field of biomedicine. This study focuses on the fabrication of hydrogels using environmentally friendly cellulosic material. Cellulose hydrogel beads were prepared by physical cross-linking in a NaOH/urea medium. Furthermore, nano polydopamine was integrated into the hydrogel matrix as functional polymers and α-mangostin was employed as an active pharmaceutical ingredient. The physicochemical properties were comprehensively analyzed using Fourier-transform infrared spectrometer, 13C cross-polarization/magic angle spinning nuclear magnetic resonance, thermogravimetric analysis, and scanning electron microscope. The drug delivery properties, including water content, swelling ratio, and drug release profiles, were evaluated. In vitro cytotoxicity against MC3T3-E1 cells was assessed using sulforhodamine B staining. All test hydrogels exhibited inhibitory activity against the growth of MC3T3-E1 cells. These results indicated the potential use of these hydrogels as a drug delivery carrier for α-mangostin in the treatment of ankylosing spondylitis.