Solid-state NMR Investigations Research Articles

Liquid-phase NMR of asphaltenes.

The present review focuses on the most recent advances in liquid-phase NMR of asphaltenes, leaving apart an overwhelming amount of publications dealing with solid-state NMR investigations in this field. Owing to the complexity of the coal-derived products, and in particular, asphaltenes, their 1H and 13C NMR spectra consist of a number of overlapping signals belonging to different hydrocarbon types. Comprehensive studies of asphaltenes by means of NMR reveal the characteristic functional groups of their fractions together with the spectral regions in which they resonate. NMR studies of asphaltenes provide a straightforward guideline for their chemical composition and that of the related coal-derived products.

Role of Cholesterol in Interaction of Ionic Liquids with Model Lipid Membranes and Associated Permeability.

In this work, we explored how the amount of cholesterol in the lipid membrane composed of phosphatidylcholine (POPC) or phosphatidylglycerol (POPG) affects the interaction with 1-dodecyl-3-methylimidazolium bromide ([C12MIM]+Br-) ionic liquids using various biophysical techniques. On interacting with the membrane, [C12MIM]+Br- leads to enhanced membrane permeability and induces membrane fusion, leading to an increase in vesicle size. The 2H-based solid-state NMR investigations of cholesterol-containing lipid membranes reveal that [C12MIM]+Br- decreases the lipid chain order parameters and counteracts the lipid condensation effect of cholesterol to some extent. Therefore, as the amount of cholesterol in the membrane increases, the membrane effect of [C12MIM]+Br- decreases. The effect of [C12MIM]+Br- on the membrane properties is more pronounced for POPC compared to that of POPG membranes. This suggests a dependence of these effects on the electrostatic interactions, indicating that the influence of [C12MIM]+Br- varies based on the lipid composition. The findings suggest that the presence of cholesterol can modulate the effect of [C12MIM]+Br- on membrane properties, with variations observed between POPC and POPG membranes, highlighting the importance of lipid composition. In short, this study provides insights into the intricate interplay between cholesterol, the lipid membrane, and the ionic liquid [C12MIM]+Br-.

Structural features and DNA binding ability of SBA-15 nanostructured silica containing amino acids or amino acid-derived drugs grafted with vanadocene complexes

Novel silica nanostructured materials, synthesized by functionalizing SBA-15 with amino acids or amino acid-derived drugs and vanadocenes, have been meticulously characterized using a range of spectroscopic and thermal techniques. Employing FTIR, solid-state UV–vis, XRF, XRD, and TGA analyses, we have unequivocally confirmed the successful functionalization of the silica carriers. The incorporation of our target molecules predominantly occurred within the pores of these silica-based systems, as evidenced by the discernible reduction in peak intensities in the corresponding diffractograms post-functionalization. Complementing these findings, solid-state 51V NMR investigations suggest a four-coordinated local symmetry around V in the final materials (S6–S8). Additionally, we conducted qualitative DNA binding tests on S7, which yielded compelling results indicating DNA adherence to the surfaces of the metallodrug-functionalized nanomaterials. In light of these results, our proposed nanosystems exhibit significant promise as potential anticancer agents.

Solid-state 2H NMR investigation of molecular motion in proton-conducting polyacrylic acid/imidazole composites

The molecular motion of imidazole (Im) in proton-conducting polyacrylic acid (PAA)/Im composite materials (PAA/xIm, where x represents the number of moles of Im per mole of the carboxyl group of PAA) was investigated using solid-state 2H NMR. For the 2H NMR analysis of polymers in which multiple constituents with different kinetic states coexist, we propose the simultaneous analysis of two 2H NMR spectra observed by the quadruple echo method using different echo intervals. The 2H NMR spectra were analyzed by superimposing simulated spectra with different jumping rates of 180° flip and isotropic rotation of Im. For PAA/0.5Im-d3, Im undergoes 180° flip below 343 K and isotropic rotation above 363 K. For PAA/1.0Im-d3, Im undergoes 180° flip below 323 K and isotropic rotation above 363 K. In the temperature range of 333–343 K, Im undergoing 180° flip and isotropic rotation coexist in PAA/1.0Im-d3. The distributions of the jumping rates of 180° flip and isotropic rotation of Im were obtained. The increase in the amount of Im enhances the jumping rate of the isotropic rotation of Im and the proton conductivity of PAA/xIm at high temperatures.

Electrochemical Sodium Storage in Hard Carbon Powder Electrodes Implemented in an Improved Cell Assembly: Insights from In-Situ and Ex-Situ Solid-State NMR.

In this work, we report on an improved cell assembly of cylindrical electrochemical cells for 23 Na in-situ solid-state NMR (ssNMR) investigations. The cell set-up is suitable for using powder electrode materials. Reproducibility of our cell assembly is analyzed by preparing two cells containing hard carbon (HC) powder as working electrode and sodium metal as reference electrode. Electrochemical storage properties of HC powder electrode derived from carbonization of sustainable cellulose are studied by ssNMR. 23 Na in-situ ssNMR monitors the sodiation/desodiation of a Na|NaPF6 |HC cell (cell 1) over a period of 22 days, showing high cell stability. After the galvanostatic process, the HC powder material is investigated by high resolution 23 Na ex-situ MAS NMR. The formation of ionic sodium species in different chemical environments is obtained. Subsequently, a second Na|NaPF6 |HC cell (cell 2) is sodiated for 11 days achieving a capacity of 220 mAh/g. 23 Na ex-situ MAS NMR measurements of the HC powder material extracted from this cell clearly indicate the presence of quasi-metallic sodium species next to ionic sodium species. This observation of quasi-metallic sodium species is discussed in terms of the achieved capacity of the cell as well as of side reactions of sodium in this electrode material.

What Is Wrong with Hyaluronic Acid Chemistry? A 15N/13C Solid-State NMR Re-Evaluation of Its Dopamine Conjugates

In this work, a systematic 15N/13C solid-state NMR investigation is performed on three dopamine (DA) conjugates of hyaluronic acid, considered in both its native (HA) and NaIO4-oxidized (HAOx) forms. Two of them, here named HAEDC-DA and HAOx-DA, have been previously introduced as covalent conjugates involving DA amine nitrogen: the former by EDC-mediated amide bond formation, and the latter by reaction of the Schiff base with the aldehyde moieties presumed to exist in HAOx. The third conjugate, HA-DA, is reported here for the first time; it is obtained by simply mixing hyaluronan with DA∙HCl at pH 5. The 15N ss-NMR spectra were found to be consistent in all the systems, and the DA molecules were found to be in their charged -NH3+ form, which contradicts the HAEDC-DA/HAOx-DA covalent bonding schemes proposed in the literature. The 13C ss-NMR results add useful new insights into the structure and interaction patterns of the conjugates. All of our findings are relevant for future practical applications, for instance in developing novel HA-based hydrogels. In addition, the present study demonstrates the importance of using the most appropriate analytical tools when investigating composite systems due to the complexity of hyaluronic acid conjugates. Solid-state NMR proved essential to answering the question in the title: actually, there is nothing wrong with hyaluronic acid chemistry; the claimed covalent bonds between DA and the HA(HAOx) chain do not exist in these systems, because the conditions for their formation do not hold in practice.

Formation of the Sub-oxide Sc4Au2O1-x and the Drastically Negative 27Al NMR Shift in Sc2Al.

During attempts to synthesize Sc4AuAl in the cubic Gd4RhIn-type structure, the solid solution Sc2Au0.5Al0.5 in the PbCl2-type structure formed instead. Subsequently, the solid solution Sc2Au1-xAlx was investigated with respect to its existence range along with the structure types formed for different compositions with x = 0, 0.25, 0.5, 0.75, and 1. According to X-ray powder diffraction studies, Sc2Al and nominal Sc2Au0.25Al0.75 crystallized in the hexagonal Ni2In-type structure (P63/mmc), while Sc2Au0.5Al0.5, Sc2Au0.75Al0.25, and Sc2Au were found to crystallize in the orthorhombic PbCl2-type structure (Pnma). The crystal structures of Sc2Au and Sc2Au0.59(1)Al0.41(1) were refined from single-crystal data (Sc2Au: a = 648.0(1), b = 467.2(1), c = 835.2(2) pm, wR2 = 0.0382, 535 F2 values, 25 variables; Sc2Au0.59(1)Al0.41(1): a = 632.48(5), b = 472.16(3), c = 848.67(6) pm, wR2 = 0.0484, 540 F2 values, 21 variables). Contamination with air during the synthesis of Sc2Au led to the discovery of a compound adopting the cubic W4Co2C-type structure (stuffed cubic Ti2Ni type). Using Sc2O3 as a defined oxygen source led to samples with high amounts of Sc4Au2O1-x. All intermetallic compounds exhibited Pauli paramagnetic behavior in the investigated temperature range of 2.1 to 300 K, and no superconductivity was observed at low temperatures and low fields. Sc2Au and Sc2Al were investigated by 27Al and 45Sc solid-state NMR investigations. For Sc2Al, one signal was found in the 27Al NMR spectra in line with the crystal structure; however, an extremely negative resonance shift of δ = -673 ppm was observed. In both compounds, two Sc resonances were observed, in line with the proposed crystal structure. Finally, it was observed that the stability of Sc2Au in air is limited. This was investigated via thermal analysis and (temperature-dependent) powder X-ray diffraction. DFT calculations helped in assessing charge analysis, electronic properties, and chemical bonding.

Ultrafast Magic Angle Spinning Solid-State NMR Spectroscopy: Advances in Methodology and Applications.

Solid-state NMR spectroscopy is one of the most commonly used techniques to study the atomic-resolution structure and dynamics of various chemical, biological, material, and pharmaceutical systems spanning multiple forms, including crystalline, liquid crystalline, fibrous, and amorphous states. Despite the unique advantages of solid-state NMR spectroscopy, its poor spectral resolution and sensitivity have severely limited the scope of this technique. Fortunately, the recent developments in probe technology that mechanically rotate the sample fast (100 kHz and above) to obtain "solution-like" NMR spectra of solids with higher resolution and sensitivity have opened numerous avenues for the development of novel NMR techniques and their applications to study a plethora of solids including globular and membrane-associated proteins, self-assembled protein aggregates such as amyloid fibers, RNA, viral assemblies, polymorphic pharmaceuticals, metal-organic framework, bone materials, and inorganic materials. While the ultrafast-MAS continues to be developed, the minute sample quantity and radio frequency requirements, shorter recycle delays enabling fast data acquisition, the feasibility of employing proton detection, enhancement in proton spectral resolution and polarization transfer efficiency, and high sensitivity per unit sample are some of the remarkable benefits of the ultrafast-MAS technology as demonstrated by the reported studies in the literature. Although the very low sample volume and very high RF power could be limitations for some of the systems, the advantages have spurred solid-state NMR investigation into increasingly complex biological and material systems. As ultrafast-MAS NMR techniques are increasingly used in multidisciplinary research areas, further development of instrumentation, probes, and advanced methods are pursued in parallel to overcome the limitations and challenges for widespread applications. This review article is focused on providing timely comprehensive coverage of the major developments on instrumentation, theory, techniques, applications, limitations, and future scope of ultrafast-MAS technology.

New salts of teriflunomide (TFM) – Single crystal X-ray and solid state NMR investigation

New salts of teriflunomide TFM (drug approved for Multiple Sclerosis treatment) with inorganic counterions: lithium (TFM_Li), sodium (TFM_Na), potassium (TFM_K), rubidium (TFM_Rb), caesium (TFM_Cs) and ammonium (TFM_NH4) were prepared and investigated employing solid state NMR Spectroscopy, Powder X-ray Diffraction PXRD and Single Crystal X-ray Diffraction (SC XRD). Crystal and molecular structures of three salts: TFM_Na (CCDC: 2173257), TFM_Cs (CCDC: 2165288) and TFM_NH4 (CCDC: 2165281) were determined and deposited. Compared to the native TFM, for all crystalline salt structures, a conformational change of the teriflunomide molecule involving about 180-degree rotation of the end group, forming an intramolecular hydrogen bond N–H⋯O is observed. By applying a complementary multi-technique approach, employing 1D and 2D solid state MAS NMR techniques, single and powder X-ray diffraction measurements, as well as the DFT-based GIPAW calculations of NMR chemical shifts for TFM_Na and TFM_Cs allowed to propose structural features of TFM_Li for which it was not possible to obtain adequate material for single crystal X-Ray measurement.

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17O and 2H NMR Analyses.

Calcium oxalate minerals of the general formula CaC2O4.xH2O are widely present in nature and usually associated with pathological calcifications, constituting up to 70–80% of the mineral component of renal calculi. The monohydrate phase (CaC2O4.H2O, COM) is the most stable form, accounting for the majority of the hydrated calcium oxalates found. These mineral phases have been studied extensively via X-ray diffraction and IR spectroscopy and, to a lesser extent, using 1H, 13C, and 43Ca solid-state NMR spectroscopy. However, several aspects of their structure and reactivity are still unclear, such as the evolution from low- to high-temperature COM structures (LT-COM and HT-COM, respectively) and the involvement of water molecules in this phase transition. Here, we report for the first time a 17O and 2H solid-state NMR investigation of the local structure and dynamics of water in the COM phase. A new procedure for the selective 17O- and 2H-isotopic enrichment of water molecules within the COM mineral is presented using mechanochemistry, which employs only microliter quantities of enriched water and leads to exchange yields up to ∼30%. 17O NMR allows both crystallographically inequivalent water molecules in the LT-COM structure to be resolved, while 2H NMR studies provide unambiguous evidence that these water molecules are undergoing different types of motions at high temperatures without exchanging with one another. Dynamics appear to be essential for water molecules in these structures, which have not been accounted for in previous structural studies on the HT-COM structure due to lack of available tools, highlighting the importance of such NMR investigations for refining the overall knowledge on biologically relevant minerals like calcium oxalates.

(De)Lithiation and Strain Mechanism in Crystalline Ge Nanoparticles.

Germanium is a promising active material for high energy density anodes in Li-ion batteries thanks to its good Li-ion conduction and mechanical properties. However, a deep understanding of the (de)lithiation mechanism of Ge requires advanced characterizations to correlate structural and chemical evolution during charge and discharge. Here we report a combined operando X-ray diffraction (XRD) and ex situ 7Li solid-state NMR investigation performed on crystalline germanium nanoparticles (c-Ge Nps) based anodes during partial and complete cycling at C/10 versus Li metal. High-resolution XRD data, acquired along three successive partial cycles, revealed the formation process of crystalline core-amorphous shell particles and their associated strain behavior, demonstrating the reversibility of the c-Ge lattice strain, unlike what is observed in the crystalline silicon nanoparticles. Moreover, the crystalline and amorphous lithiated phases formed during a complete lithiation cycle are identified. Amorphous Li7Ge3 and Li7Ge2 are formed successively, followed by the appearance of crystalline Li15Ge4 (c-Li15Ge4) at the end of lithiation. These results highlight the enhanced mechanical properties of germanium compared to silicon, which can mitigate pulverization and increase structural stability, in the perspective for developing high-performance anodes.

Surface and structural characterization of Cu-exchanged hydroxyapatites and their application in H2O2 electrocatalytic reduction

We report on the preparation of hydroxyapatite (HA) nanoparticles with high specific surface area, terminated with calcium-rich {010} facets, and their subsequent surface functionalization with copper by cationic exchange with copper nitrate solutions at different concentrations. Elemental analysis highlighted a progressive increase of the amount of copper incorporated into the HA, reaching a maximum of ∼ 7 wt%. A combined X-ray diffraction and solid-state NMR investigation showed no significant structural differences after the Cu functionalization, confirming that the copper exchange occurs mainly at the surface until saturation and, for the higher Cu concentrations, also in the sub-surface/bulk layers of the material, without altering the HA crystal structure. The gradual substitution of surface Ca2+ by Cu2+ was studied also by IR spectroscopy using carbon monoxide as probe molecule. Finally, we assessed the catalytic activity of the materials testing the electrochemical reduction of H2O2 by cyclic voltammetry. We observed a progressive increase in catalytic activity correlated with the amount of Cu, suggesting the possible application of copper-exchanged HA as electrochemical H2O2 sensors.

Epoxy resin/TiO2 nanocomposites prepared by the Reactive Suspension Method: Dynamic-mechanical properties and their prediction by theoretical models

In this study epoxy resin/TiO2 nanocomposites have been prepared according to the Reactive Suspension Method, to obtain TiO2 nanoparticles (NPs) covalently bonded to the macromolecular network. After the chemical-physical characterization of both NPs and polymeric matrix, the dynamic-mechanical properties (storage modulus as a function of the temperature) of the nanocomposites have been studied. In particular, the experimental storage modulus in the rubbery state has been found significantly higher than the value predicted by the generalized Kerner equation. This has been rationalized considering that the inorganic NPs act as additional cross-linking points, as confirmed by the solid-state NMR investigations, leading to a very high and unexpected increase of the stiffness. Consequently, the experimental data have been also fitted using the Halpin-Tsai equation, which has allowed to obtain suitable predictions of the storage modulus by adjusting the so-called reinforcing geometry factor. By the proposed approach has been possible to incorporate in the Halpin-Tsai model a factor that considers the contribution due to the presence of filler/matrix covalent bonds and to obtain more accurate predictions.

Polysaccharide Based Polymers Produced by Scabby Cankered Cactus Pear (Opuntia ficus-indica L.) Infected by Neofusicoccum batangarum: Composition, Structure, and Chemico-Physical Properties.

Neofusiccocum batangarum is the causal agent of scabby canker of cactus pear (Opuntia ficus-indica L.). The symptoms of this disease are characterized by crusty, perennial cankers, with a leathery, brown halo. Characteristically, a viscous polysaccharide exudate, caking on contact with air, leaks from cankers and forms strips or cerebriform masses on the surface of cactus pear cladodes. When this polysaccharide mass was partial purified, surprisingly, generated a gel. The TLC analysis and the HPLC profile of methyl 2-(polyhydroxyalkyl)-3-(o-tolylthiocarbomoyl)-thiazolidine-4R-carboxylates obtained from the mixture of monosaccharides produced by acid hydrolysis of the three EPSs examined in this research work [the polysaccharide component of the exudate (EPSC) and the EPSs extracted from asymptomatic (EPSH) and symptomatic (EPSD) cladodes] showed the presence of d-galactose, l-rhamnose, and d-glucose in a 1:1:0.5 ratio in EPSC while d-galactose, l-rhamnose, d-glucose, and d-xylose at the same ratio were observed in EPSH and EPSD. The presence of uronic acid residues in EPSC was also showed by solid state NMR and IR investigation. Furthermore, this manuscript reports the chemical-physical characterization of the gel produced by the infected cactus pear.

Impact of Lipid Ratio on the Permeability of Mixed Phosphatidylcholine/Phosphatidylglycerol Membranes in the Presence of 1-Dodecyl-3-methylimidazolium Bromide Ionic Liquid.

We have studied the impact of the lipid ratio on the membrane permeability of mixed phosphatidylcholine (POPC)/phosphatidylglycerol (POPG) membranes induced by 1-dodecyl-3-methylimidazolium bromide ([C12MIM]+Br-) ionic liquid by evaluating the role of affinity and architecture of the phospholipid bilayer. Nine different model membranes composed of negatively charged POPG and zwitterionic POPC lipids mixed in molar ratios of 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, and 1:9 have been studied. The membrane permeability of each composition has been evaluated using fluorescence-based dye leakage assays. Despite having the highest membrane affinity, POPG-rich membranes doped with 10 and 20 mol % POPC are found to be the least permeable. 31P- and 2H-based solid-state NMR investigations reveal that the minor POPC component is homogeneously dispersed in the PG/PC (8:2) membrane. In contrast, the lipids seem to be segregated into POPG- and POPC-rich domains in the complementary PG/PC (2:8) composition. Although [C12MIM]+ cations have a stronger interaction with the POPG component in the mixed membranes, their insertion has a limited impact on the overall structure and dynamics of the PG/PC (8:2) composition.

Solid-State NMR Investigations of Extracellular Matrixes and Cell Walls of Algae, Bacteria, Fungi, and Plants

Extracellular matrixes (ECMs), such as the cell walls and biofilms, are important for supporting cell integrity and function and regulating intercellular communication. These biomaterials are also of significant interest to the production of biofuels and the development of antimicrobial treatment. Solid-state nuclear magnetic resonance (ssNMR) and magic-angle spinning-dynamic nuclear polarization (MAS-DNP) are uniquely powerful for understanding the conformational structure, dynamical characteristics, and supramolecular assemblies of carbohydrates and other biomolecules in ECMs. This review highlights the recent high-resolution investigations of intact ECMs and native cells in many organisms spanning across plants, bacteria, fungi, and algae. We spotlight the structural principles identified in ECMs, discuss the current technical limitation and underexplored biochemical topics, and point out the promising opportunities enabled by the recent advances of the rapidly evolving ssNMR technology.

Solid-State NMR and Raman Spectroscopic Investigation of Fluoride-Substituted Apatites Obtained in Various Thermal Conditions.

Fluoride-substituted apatites were synthesized by the standard sol-gel method and then calcined at three different temperatures: 800 °C, 1000 °C, and 1200 °C. Using a similar method, hydroxyapatite was synthesized and used as a reference material. The obtained powders were characterized by physicochemical methods: powder X-ray diffractometry, Raman spectroscopy, transmission electron microscopy, and solid-state nuclear magnetic resonance. All these methods allowed to identify additional α-TCP phase (tricalcium phosphate) in the HAP samples heated at 1000 °C and 1200 °C while fluoridated apatites turned out to be thermally stable. Moreover, Raman spectroscopy and NMR allowed to establish that the powders substituted with fluoride ions are not pure fluorapatite and contain OH- groups in the crystal structure. All the obtained materials had crystals with a shape similar to that of biological apatite.

3D Printing of Soy Protein- and Gluten-Based Gels Facilitated by Thermosensitive Cocoa Butter in a Model Study

In this study, formulation of soy protein- and gluten-based gel materials for 3D printing in a model study has been successfully developed employing thermosensitive cocoa butter to investigate its feasibility for preparing meat analogues. The influence of protein, starch, and sodium alginate on extrusion formability and printing accuracy was investigated. The extrusion formability of doughs of soy protein isolate was notably better than that of pea protein. Addition of appropriate amounts of cocoa butter, Tween-80, and sodium alginate was essential to achieve superior 3D printing performance. Thermosensitive cocoa butter provided fluidity to the doughs during 3D printing above room temperature and retained the shape upon solidification at room temperature. SEM-EDS, FT-IR, and solid-state NMR investigations revealed that the hydrogen bonding interaction of the soy protein and gluten network generated the fundamental continuous fibrous architecture of the gels. The developed strategy in this study would be valuable for formulating materials for 3D printing.

Solid State NMR Investigation for Molecular States of Specialized Formulation to Improve the Water Solubility of Poorly Water-soluble Drugs

70-90% of recently developed new drug candidates are poorly soluble in water, which creates a series of thorny challenges in developing its oral dosage forms, resulting in low bioavailability. In pre-formulation study, various specialized formulations have been developed to improve drug solubility. Intermolecular interactions between drug and excipients in the formulations can modify the drug state and achieve the improvement of drug solubility. Therefore, the understanding of intermolecular interaction is essential to design formulations with higher quality and to assure the quality as a pharmaceutical product. Solid-state NMR has attracted much attention as a promising method to evaluate the molecular state of a drug and the interaction between a drug and excipient in its formulation. I have applied solid-state NMR and its characteristic technique, namely magic-angle spinning (MAS), for various specialized formulations including amorphous solid dispersion, supersaturated solution, drug-loaded organic nanotube, and drug nanosuspension. The intermolecular interactions of drug and excipient in amorphous solid dispersion have been identified by 13C and 15N solid-state NMR. High-resolution MAS determined the interaction modes of drug and excipient in a supersaturated solution. The two-step dissolution profile of drug from organic nanotube was understood, based on the molecular states revealed by the combination of various solid-state NMR techniques. A suspended-state NMR clarified the nanostructure of drug nanoparticles dispersed in water. It is expected that more qualified pharmaceutical formulations with improved drug solubility can be designed based on the remarkable development of recent solid-state NMR technology.

Exploring the interplay of mucin with biologically-relevant amorphous magnesium-calcium phosphate nanoparticles

HypothesisIt has been recently shown that, in our organism, the secretions of Ca2+, Mg2+ and phosphate ions lead to the precipitation of amorphous magnesium-calcium phosphate nanoparticles (AMCPs) in the small intestine, where the glycoprotein mucin is one of the most abundant proteins, being the main component of the mucus hydrogel layer covering gut epithelium. Since AMCPs precipitate in vivo in a mucin-rich environment, we aim at studying the effect of this glycoprotein on the formation and features of endogenous-like AMCPs. ExperimentsAMCPs were synthesized from aqueous solution in the presence of different concentrations of mucin, and the obtained particles were characterised in terms of crystallinity, composition and morphology. Solid State NMR investigation was also performed in order to assess the interplay between mucin and AMCPs at a sub-nanometric level. FindingResults show that AMCPs form in the presence of mucin and the glycoprotein is efficiently incorporated in the amorphous particles. NMR indicates the existence of interactions between AMCPs and mucin, revealing how AMCPs in mucin-hybrid nanoparticles affect the features of both proteic and oligosaccharidic portions of the glycoprotein. Considering that the primary function of mucin is the protection of the intestine from pathogens, we speculate that the nature of the interaction between AMCPs and mucin described in the present work might be relevant to the immune system, suggesting a novel type of scenario which could be investigated by combining physico-chemical and biomedical approaches.