Syntheses, Crystal Structures and Characterization of Two New Lanthanide Mercury Halide Compounds.

Two new lanthanide mercury halide compounds with isonicotinic acid as a ligand, namely, [Gd(HIA)2(IA)(H2O)2(HgCl2)]n(nHgCl4)·3nH2O (1) (HIA = isonicotinic acid) and {[Nd(HIA)3(DMF)(H2O)]n}[(Hg4Br11)n](2HgBr2)(nBr)·nH3O·0.5nH2O (2) (DMF = N,N'-Dimethylformamide), were synthesized by means of solvothermal reactions and characterized by single-crystal X-ray diffraction. Compound 1 is characterized by a two-dimensional (2-D) layer-like structure, while compound 2 features a one-dimensional (1-D) chain-like structure.

Directional Breathing of Fullerene Cages: Crystallographic Evidence for Endohedral C-Triggered Elongation of (6)-C Cage.

The interplay between fullerene cages and endohedral units is crucial for the stability and properties of endohedral metallofullerenes (EMFs). However, clear visualization of such an interplay remains rare due to the scarcity of suitable comparative EMFs molecules. Here, we report for the first time a unique cage elongation along the cycloparaphenylene belt, induced by a direct C insertion within a (6)-C cage.

A numerical simulation study of airway flow: Impact of bronchial stenosis.

Obstructive lung diseases, marked by airway stenosis, are chronic and pose significant mortality risks. This study aims to analyze airflow patterns in obstructed bronchi, comparing them to healthy airways during tidal breathing to improve our comprehension of disease effects on respiratory function. The current studies mostly overlook the specific morphology of the patient's upper airway or the elastic deformation of the airway soft tissues, which results in the existing results not being sufficient to effectively guide surgical treatment.

Comparative analysis of airflow dynamics and sputum expulsion during cough in healthy and bronchial stenosis respiratory tract.

Bronchial stenosis impacts cough mechanisms and respiratory function. This study used MIMICS and Fluent to construct and simulate a 3D airway model of an elderly female patient with bronchial stenosis. Utilizing dynamic mesh and fluid-structure interaction, airflow during coughing was analyzed, including velocity, wall shear stress, and deformation.

Preparation, Structures, Photoluminescence and Semiconductive Properties of Two Novel Lanthanide Mercury Materials with a 3-D Framework Structure.

Two novel lanthanide mercury materials, [Gd(IA)3(H3O)2Hg3Br6]n·2nCl (1) and [La(IA)3(H3O)2Hg3Br6]n·2nCl (2) (IA = isonicotinic anion), have been prepared under solvothermal conditions and characterized by single-crystal X-ray diffraction techniques. They are isomorphic and characterized by a three-dimensional (3-D) framework structure. The lanthanide ions are bound by eight oxygen atoms to exhibit a square antiprismatic geometry.

A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage.

Reducing inter-spin distance can enhance magnetic interactions and allow for the realization of outstanding magnetic properties. However, achieving reduced distances is technically challenging. Here, we construct a 3d-4f metal cluster (DyVN) inside a C cage, affording a heretofore unseen metallofullerene containing both paramagnetic 3d and 4f metal ions.

Stabilizing a non-IPR (13333)-C cage with LuC/LuO: the importance of encaged non-metallic elements.

A difference in encaged non-metallic element (, C O) leads to a clear change of intramolecular interactions and shifts in redox potentials of LuC@(13333)-C and LuO@(13333)-C, as a result of their distinct molecular orbital energy levels. Different from these two endoherals whose HOMOs are located on the cage, experimentally absent Lu@(13333)-C possesses a HOMO predominantly delocalized on the internal Lu-Lu bond, accompanied by a much smaller HOMO-LUMO gap, suggesting that the presence of a non-metallic unit broadens the electrochemical gaps and consequently improves the kinetic stability. These findings shed light on the role of non-metallic moieties in clusterfullerenes, providing valuable insights into the stability and properties of metallofullerenes.

Ultrahigh Capacity from Complexation-Enabled Aluminum-Ion Batteries with C as the Cathode.

Restricted by the available energy storage modes, currently rechargeable aluminum-ion batteries (RABs) can only provide a very limited experimental capacity, regardless of the very high gravimetric capacity of Al (2980 mAh g ). Here, a novel complexation mechanism is reported for energy storage in RABs by utilizing 0D fullerene C as the cathode. This mechanism enables remarkable discharge voltage (≈1.

Regioselective Radical Reaction of Monometallofullerene Y@C(9)-C With N-arylbenzamidine Mediated by Silver Carbonate.

A novel radical reaction of monometallofullerene Y@C(9)-C with N-arylbezamidine () is successfully conducted through catalysis with silver carbonate. The high-performance liquid chromatographic and mass spectrum results demonstrate that the reaction is highly regioselective to afford only one monoadduct () with an imidazoline group added on C cage, and computations through density functional theory reveal the addition group is attached to a specific [5, 6]-bond (C20-C76) near the Y atom. Furthermore, the analysis of prymidalization angle of the carbon atoms demonstrates the geometry of carbon cage is in favor of the regioselective formation of isomer (20, 76).

The degradable performance of bile-duct stent based on a continuum damage model: A finite element analysis.

Biomedical magnesium alloy stents have become a hot bed of research focus in interventional therapy for nonvascular diseases. In this study, a numerical model for a balloon-expandable bile duct stent made of magnesium alloy with laser sculpture is developed to predict the effects of the degradation of the stent on the biomechanical behavior in the stent-bile duct coupling system. Based on a continuum damage model, the degradable model of the stent is built to understand its performance in an idealized bile duct as it is subject to corrosion over time.

Trapping an unprecedented TiC unit inside the icosahedral C fullerene: a crystallographic survey.

The sub-nanometer cavity of fullerene cages is an ideal platform to accommodate otherwise unstable species for accurate structural characterization with, for example, rather accurate single crystal X-ray diffraction (XRD) crystallography. Herein, we report the successful entrapment of an isolated TiC moiety inside the icosahedral-C cage to form TiC@I-C an arc-evaporation process in the gas phase. The single crystal XRD crystallographic results unambiguously reveal that the C-unit adopts an unprecedented cyclopropane-like structure which coordinates with the three titanium atoms in an unexpected fashion where the triangular C-unit is nearly perpendicular to the Ti-plane.

Regioselective Synthesis, Crystallographic Characterization, and Electrochemical Properties of Pyrazole- and Pyrrole-Ring-Fused Derivatives of Y @C (8)-C.

Chemical modification of endohedral metallofullerenes (EMFs) is an efficient strategy to realize their ultimate applications in many fields. Herein, we report the highly regioselective and quantitative mono-formation of pyrazole- and pyrrole-ring-fused derivatives of the prototypical di-EMF Y @C (8)-C , that is, Y @C (8)-C (C N H ) and Y @C (8)-C (C NH ), from the respective 1,3-dipolar reactions with either diphenylnitrilimine or N-benzylazomethine ylide, without the formation of any bis- or multi-adducts. Crystallographic results unambiguously reveal that only one [6,6]-bond out of the twenty-five different types of nonequivalent C-C bonds of Y @C (8)-C is involved in the 1,3-dipolar reactions.

Highly regioselective complexation of tungsten with Eu@C/Eu@C: interplay between endohedral and exohedral metallic units induced by electron transfer.

Interactions between the inner and outer units through a fullerene cage are of fundamental importance for the creation of molecular spintronics and machines, but the mechanism of such through-cage interplay is still unclear. In this work, we have designed and synthesized two prototypical compounds which contain only a single europium atom inside the cage and merely a tungsten atom coordinating outside to clarify the interactions between the endohedral and exohedral metallic units. They are obtained by reacting a tungsten complex W(CO)(PhPCHPPh) () with the corresponding metallofullerenes in a highly regioselective manner ( for Eu@ (5)-C and for Eu@ (13)-C).

Intermolecular packing and charge transfer in metallofullerene/porphyrin cocrystals.

Charge transfer in metallofullerene/porphyrin cocrystals is revealed for the first time. Originated from the different solvents for crystallization, distinct stacking manners are presented in the two types of cocrystals. It is demonstrated that intermolecular packing, next to the nature of the corresponding electron donors and acceptors, dominates the charge transfer processes.

Crystallographic identification of Eu@C (2 = 88, 86 and 84): completing a transformation map for existing metallofullerenes.

Revealing the transformation routes among existing fullerene isomers is key to understanding the formation mechanism of fullerenes which is still unclear now because of the absence of typical key links. Herein, we have crystallographically identified four new fullerene cages, namely, (27)-C, (7)-C, (13)-C and (11)-C, in the form of Eu@C , which are important links to complete a transformation map that contains as many as 98% (176 compounds in total) of the reported metallofullerenes with clear cage structures (C , 2 = 86-74). Importantly, the mutual transformations between the metallofullerene isomers included in the map require only one or two well-established steps (Stone-Wales transformation and/or C insertion/extrusion).

Oxygen-Delivery Materials: Synthesis of an Open-Cage Fullerene Derivative Suitable for Encapsulation of H O and O.

An open-cage [60]fullerene was prepared through a multiple-step sequence based on peroxide-mediated cage-opening reactions. Key steps include repeated C -sensitized singlet-oxygen oxidation of electron-rich amino enol double bonds to form two lactone and two lactam moieties on the rim of the orifice. Single-crystal X-ray analysis shows that the 22-membered orifice has an ellipsoid shape with the major axis at 6.

Numerical research on the biomechanical behaviour of braided stents with different end shapes and stent-oesophagus interaction.

Quasi-static and dynamic numerical analyses are carried out by referring to computational models of commercial self-expandable braided stents with 3 commonly used end shapes, to evaluate the influence of different end shapes of stent on the biomechanical interaction between stent and oesophagus. The end shape has no influence on the equivalent stress, but has a great influence on the contact stress in the narrowest zone of the oesophagus-neoplasm system. However, the end shapes have significant effect on the equivalent stress and the contact stress in the healthy area of the oesophagus in contact with the stent ends.

Facile Access to YC (2n = 92-130) and Crystallographic Characterization of YC@C(1660)-C: A Giant Nanocapsule with a Linear Carbide Cluster.

A series of giant metallofullerenes YC (2n = 92-130) have been successfully obtained through the treatment of the fraction enriched by 1,2-dichlorobenzene with SnCl. Subsequent chromatographic separation gives a pure sample with a composition of YC. Crystallographic results reveal that this endohedral takes the carbide form, namely YC@C(1660)-C, representing as the largest metallofullerene that has been characterized by crystallography to date.

Lu@C (2n = 82, 84, 86): Crystallographic Evidence of Direct Lu-Lu Bonding between Two Divalent Lutetium Ions Inside Fullerene Cages.

Although most of the MC-type metallofullerenes (EMFs) tend to form carbide cluster EMFs, we report herein that Lu-containing EMFs LuC (2n = 82, 84, 86) are actually dimetallofullerenes (di-EMFs), namely, Lu@C(6)-C, Lu@C(8)-C, Lu@D(23)-C, and Lu@C(9)-C. Unambiguous X-ray results demonstrate the formation of a Lu-Lu single bond between two lutetium ions which transfers four electrons in total to the fullerene cages, thus resulting in a formal divalent state for each Lu ion. Population analysis indicates that each Lu atom formally donates a 5d electron and a 6s electron to the cage with the remaining 6s electron shared with the other Lu atom to form a Lu-Lu single bond so that only four electrons are transferred to the fullerene cages with the formal divalent valence for each lutetium ion.

Isolation and Crystallographic Characterization of the Labile Isomer of Y@C82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes.

Although the major isomers of M@C82 (namely M@C2v (9)-C82 , where M is a trivalent rare-earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C82 isomer, unambiguously assigned as Y@Cs (6)-C82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs (6)-C82 .

Regioselective Synthesis and Crystallographic Characterization of Isoxazoline-Ring-Fused Derivatives of Sc3N@Ih-C80 and C60.

Highly regioselective 1,3-dipolar cycloaddition of 3,5-dichloro-2,4,6-trimethoxybenzonitrile oxide (1) to Sc3N@Ih-C80 or C60 affords the corresponding isoxazoline-ring-fused derivatives Sc3N@Ih-C80(C10H9O4NCl2) (2a) and C60(C10H9O4NCl2) (2b). 2a represents the first example of an endohedral metallofullerene derivative with an isoxazoline ring. Crystallographic and NMR spectroscopic studies reveal a [5,6]-bond addition pattern in 2a but a [6,6]-bond addition manner in 2b.

W(CO)3(Ph2PC2H4PPh2)(η(2)-Sc3N@Ih-C80/Sc3N@D5h-C80): regioselective synthesis and crystallographic characterization of air-stable mononuclear complexes of endohedral fullerenes.

The organometallic chemistry of endohedral metallofullerenes has lagged far behind that of empty fullerenes. Herein, we report a highly regioselective coordination reaction involving two Sc3N@C80 isomers and W(CO)4(Ph2PC2H4PPh2) (1), which affords only one mononuclear complex for each Sc3N@C80 isomer (2a for Sc3N@Ih-C80 and 2b for Sc3N@D5h-C80). X-ray results demonstrate that the tungsten center coordinates with the cages in an η(2) fashion on a [6,6]-bond in both cases, forming the first derivatives with a closed three membered ring for Sc3N@C80.

Induction of Autophagy interferes the tachyzoite to bradyzoite transformation of Toxoplasma gondii.

Autophagy process in Toxoplasma gondii plays a vital role in regulating parasite survival or death. Thus, once having an understanding of certain effects of autophagy on the transformation of tachyzoite to bradyzoite this will allow us to elucidate the function of autophagy during parasite development. Herein, we used three TgAtg proteins involved in Atg8 conjugation system, TgAtg3, TgAtg7 and TgAtg8 to evaluate the autophagy level in tachyzoite and bradyzoite of Toxoplasma in vitro based on Pru TgAtg7-HA transgenic strains.