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Here, we present elegant examples of a precise determination of the pathways for proton transport.We present for the first time a method for the preparation of magnetic halloysite nanotubes (HNT) by loading of preformed superparamagnetic magnetite nanoparticles (SPION) of diameter size ∼6 nm with a hydrodynamic diameter of ∼10 nm into HNT. We found that the most effective route to reach this goal relies on the modification of the inner lumen of HNT by tetradecylphosphonic acid (TDP) to give HNT-TDP, followed by the loading with preformed oleic acid (OA)-stabilized SPION. Transmission electron microscopy evidenced the presence of highly crystalline magnetic nanoparticles only in the lumen, partially ordered in chainlike structures. Conversely, attempts to obtain the same result by exploiting either the positive charge of the HNT inner lumen employing SPIONs covered with negatively charged capping agents or the in situ synthesis of SPION by thermal decomposition were not effective. HNT-TDP were characterized by infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), and ζ-potential, and all of the techniques confirmed the presence of TDP onto the HNT. Moreover, the inner localization of TDP was ascertained by the use of Nile Red, a molecule whose luminescence is very sensitive to the polarity of the environment. Cytoskeletal Signaling activator The free SPION@OA (as a colloidal suspension and as a powder) and SPION-in-HNT powder were magnetically characterized by measuring the ZFC-FC magnetization curves as well as the hysteresis cycles at 300 and 2.5 K, confirming that the super-paramagnetic behavior and the main magnetic properties of the free SPION were preserved once embedded in SPION-in-HNT.The carbon monoxide (CO)-photoreleasing molecule [Ru(Me3[9]aneN3)(bpy)(CO)]2+ (RuCO 2+ ; bpy = 2,2′-bipyridine) was prepared and structurally characterized. The photochemical behavior was studied in unprecedented detail for this type of system, using a combination of steady-state and ultrafast transient absorption experiments, which unveiled that 3MLCT and 3dd excited states participate in the decay cascade of photoexcited RuCO 2+ . Theoretical calculations yield a consistent picture, providing details of the electronic structure of the transient species involved. Our results suggest that the photorelease of CO involves excited states of different electronic nature that are populated sequentially and in parallel. This complex scenario strengthens the idea that the rational design of a good photoCORM is a difficult task to carry out solely using the tools provided by chemical intuition it is necessary to control by design factors that favor the population of specific photoactive electronic states with respect to those that are not.The synthesis of monomeric octahedral complexes constructed around a TiO4N2 core bearing neocuproine derivatives is detailed. These architectures follow the [Ti(1)2(N-N)] general formulas, where 1 is the 6,6′-diphenyl-2,2′-biphenolato ligand and N-N is a 1,10-phenanthroline derivative. Single-crystal analysis revealed that the neocuproine-based ligands within these architectures adopt a nonplanar geometry. The distortion of these aromatic diimine systems has been quantified through measurement of a torsion angle (α) and a dihedral angle (β) defined by two planes within the aromatic diimine molecule (π1 and π2), permitting one to evaluate the twisting and bending of a coordinated nitrogen ligand, respectively. Next, the scope of this investigation was extended to the synthesis of a dimeric architecture, [Ti2(1)4(3)], where 3 is the 5,5′-bis(neocuproine) ligand. Again, a strong distortion of the neocuproine fragments was characterized in the crystalline state for such a complex. The UV-visible properties of these complexes were interpreted with the help of time-dependent density functional theory calculations. The solution behavior as well as good hydrolytic stability of these species has been established.Macrophage inflammation and maturation into foam cells, following the engulfment of oxidized low-density lipoproteins (oxLDL), are major hallmarks in the onset and progression of atherosclerosis. Yet, chronic treatments with anti-inflammatory agents, such as methotrexate (MTX), failed to modulate disease progression, possibly for the limited drug bioavailability and plaque deposition. Here, MTX-lipid conjugates, based on 1,2-distearoyl-sn-glycero-3-phosphoethanolamine (DSPE), were integrated in the structure of spherical polymeric nanoparticles (MTX-SPNs) or intercalated in the lipid bilayer of liposomes (MTX-LIP). Although, both nanoparticles were colloidally stable with an average diameter of ∼200 nm, MTX-LIP exhibited a higher encapsulation efficiency (>70%) and slower release rate (∼50% at 10 h) compared to MTX-SPN. In primary bone marrow derived macrophages (BMDMs), MTX-LIP modulated the transcellular transport of oxLDL more efficiently than free MTX mostly by inducing a 2-fold overexpression of ABCA1 (regulating oxLDL efflux), while the effect on CD36 and SRA-1 (regulating oxLDL influx) was minimal. Furthermore, in BMDMs, MTX-LIP showed a stronger anti-inflammatory activity than free MTX, reducing the expression of IL-1β by 3-fold, IL-6 by 2-fold, and also moderately of TNF-α. In 28 days high-fat-diet-fed apoE-/- mice, MTX-LIP reduced the mean plaque area by 2-fold and the hematic amounts of RANTES by half as compared to free MTX. These results would suggest that the nanoenhanced delivery to vascular plaques of the anti-inflammatory DSPE-MTX conjugate could effectively modulate the disease progression by halting monocytes’ maturation and recruitment already at the onset of atherosclerosis.The development of multifunctional hydrogels with high strength and stretchability is one of the most important topics in soft-matter research owing to their potential applications in various fields. In this work, a dual physically cross-linked network was designed for the fabrication of ultrastretchable tough hydrogels. The hydrogels were prepared through in situ polymerization of acrylic acid and acrylamide in the presence of positively charged quaternary poly(ethylene imine) (Q-PEI) and micelle-forming Pluronic F127 diacrylate, thus introducing electrostatic interactions between the positively charged Q-PEI and negatively charged poly(acrylic acid-co-acrylamide). For further mechanical reinforcement, Ca2+ and Cu2+ ions were introduced into the hydrogel network to construct coordination bonds, significantly enhancing tensile strength as well as stretchability. The hydrogel prepared with Ca2+ ion coordination bonds was found to be stretchable to 108 times its original length and exhibited a maximum toughness of 177 MJ·m-3, representing one of the most robust systems with both extraordinary toughness and superstretchability prepared to date.