Multifacets of Fullerene-Metal Clusters: From Fundamental to Application.

ConspectusBuckminsterfullerene, C60, was discovered through a prominent mass peak containing 60 atoms produced from laser vaporization of graphite, driven by Kroto's interest in understanding the formation mechanisms of carbon-containing molecules in space. Inspired by the geodesic dome-shaped architecture designed by Richard Buckminster Fuller, after whom the particle was named, C60 was found to have a football-shaped structure comprising 20 hexagons and 12 pentagons. It sparked worldwide interest in understanding this new carbon allotrope, resulting in the awarding of the Noble Prize in Chemistry to Smalley, Kroto, and Curl in 1996.Intrinsically, C60 is an exceptional species because of its high stability and electron-accepting ability and its structural tunability by decorating or substituting either on its exterior surface or interior hollow cavity. For example, metal-decorated fullerene complexes have found important applications ranging from superconductivity, nanoscale electronic devices, and organic photovoltaic cells to catalysis and biomedicine. Compared to the large body of studies on atoms and molecules encapsulated by C60, studies on the exteriorly modified fullerenes, i.e., exohedral fullerenes, are scarcer. Surprisingly, to date, uncertainty exists about a fundamental question: what is the preferable exterior binding site of different kinds of single atoms on the C60 surface?In recent years, we have developed an experimental protocol to synthesize the desired fullerene-metal clusters and to record their infrared spectra via messenger-tagged infrared multiple photon dissociation spectroscopy. With complementary quantum chemical calculations and molecular dynamics simulations, we determined that the most probable binding site of a metal, specifically a vanadium cation, on C60 is above a pentagonal center in an η5 fashion. We explored the bonding nature between C60 and V+ and revealed that the high thermal stability of this cluster originates from large orbital and electrostatic interactions. Through comparing the measured infrared spectra of [C60-Metal]+ with the observational Spitzer data of several fullerene-rich planetary nebulae, we proposed that the complexes formed by fullerene and cosmically abundant metals, for example, iron, are promising carriers of astronomical unidentified spectroscopic features. This opens the door for a real consideration of Kroto's 30-year-old hypothesis that complexes involving cosmically abundant elements and C60 exhibit strong charge-transfer bands, similar to those of certain unidentified astrophysical spectroscopic features. We compiled a VibFullerene database and extracted a set of vibrational frequencies and intensities for fullerene derivatives to facilitate their potential detection by the James Webb Space Telescope. In addition, we showed that upon infrared irradiation C60V+ can efficiently catalyze water splitting to generate H2. This finding is attributed to the novel geometric-electronic effects of C60, acting as "hydrogen shuttle" and "electron sponge", which illustrates the important role of carbon-based supports in single-atom catalysts. Our work not only unveils the basic structures and bonding nature of fullerene-metal clusters but also elucidates their potential importance in astrophysics, astrochemistry, and catalysis, showing the multifaceted character of this class of clusters. More exciting and interesting aspects of the fullerene-metal clusters, such as ultrafast charge-transfer dynamics between fullerene and metal and their relevance to designing hybrid fullerene-metal junctions for electronic devices, are awaiting exploration.

Direct reduction of NO into N2 catalyzed by fullerene-supported rhodium clusters.

Catalytic conversion of NO has long been a focus of atmospheric pollution control and diesel vehicle exhaust treatment. Rhodium is one of the most effective metals for catalyzing NO reduction, and understanding the nature of the active sites and underlying mechanisms can help improve the design of Rh-based catalysts towards NO reduction. In this work, we investigated the detailed catalytic mechanisms for the direct reduction of NO to N2 by fullerene-supported rhodium clusters, C60Rh4+, with density functional theory calculations. We found that the presence of C60 facilitates the smooth reduction of NO into N2 and O2, as well as their subsequent desorption, recovering the catalyst C60Rh4+. Such a process fails to be completed by free Rh4+, emphasizing the critical importance of C60 support. We attribute the novel performance of C60Rh4+ to the electron sponge effect of C60, providing useful guidance for designing efficient catalysts for the direct reduction of NO.

Guest-Regulated Generation of Reactive Oxygen Species from Porphyrin-Based Multicomponent Metallacages for Selective Photocatalysis.

The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host-guest chemistry of porphyrin-based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage (6) can generate singlet oxygen (1O2) effectively via excited energy transfer, while its complex with C70 (6⊃C70) opens a pathway for electron transfer to promote the formation of superoxide anion (O2⋅-), producing both 1O2 and O2⋅-. The addition of 4,4'-bipyridine (BPY) to complex 6⊃C70 forms a more stable complex (6⊃BPY) via the coordination of the Zn-porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1O2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6⊃BPY, while they are oxidized into benzoic acids when 6⊃C70 is employed as the photosensitizing agent. This study demonstrates a highly efficient strategy that utilizes the host-guest chemistry of metallacages to regulate the generation of reactive oxygen species for selective photooxidation reactions, which could promote the utilization of metallacages and their related host-guest complexes for photocatalytic applications.

Pentagon, Hexagon, or Bridge? Identifying the Location of a Single Vanadium Cation on Buckminsterfullerene Surface.

Buckminsterfullerene C60 has received extensive research interest since its discovery. In addition to its interesting intrinsic properties of exceptional stability and electron-accepting ability, the broad chemical tunability by decoration or substitution on the C60-fullerene surface makes it a fascinating molecule. However, to date, there is uncertainty about the binding location of such decorations on the C60 surface, even for a single adsorbed metal atom. In this work, we report the gas-phase synthesis of the C60V+ complex and its in situ characterization by mass spectrometry and infrared spectroscopy with the help of quantum chemical calculations and molecular dynamics simulations. We identify the most probable binding position of a vanadium cation on C60 above a pentagon center in an η5-fashion, demonstrate a high thermal stability for this complex, and explore the bonding nature between C60 and the vanadium cation, revealing that large orbital and electrostatic interactions lie at the origin of the stability of the η5-C60V+ complex.

Synthesis of KVPO4F/Carbon Porous Single Crystalline Nanoplates for High-Rate Potassium-Ion Batteries.

With high theoretical capacity and operating voltage, KVPO4F is a potential high energy density cathode material for potassium-ion batteries. However, its performance is usually limited by F loss, poor electronic conductivity, and unsteady electrode/electrolyte interface. Herein, a simple one-step sintering process is developed, where vanadium-oxalate-phosphite/phosphate frameworks and fluorinated polymer are used to synthesize carbon-coated KVPO4F nanoplates. It is found that the V-F-C bond generated by fluorinated-polymer-derived carbon at the interface of KVPO4F/C nanoplates diminishes the F loss, as well as enhances K-ions migration ability and the electronic conductivity of KVPO4F. The as-synthesized KVPO4F/C cathode delivers a reversible capacity of 106.5 mAh g-1 at 0.2 C, a high working voltage of 4.28 V, and a rate capability with capacity of 73.8 mAh g-1 at the ultrahigh current density of 100 C. In addition, a KVPO4F/C//soft carbon full cell exhibits a high energy density of 235.5 Wh kg-1.

Geometries, electronic structures, and bonding properties of endohedral Group-14 Zintl clusters TM@E10 (TM = Fe, Co, Ni; E = Ge, Sn, Pb).

The geometries, electronic structures, and bonding properties of the title endohedral Zintl clusters have been studied by using ab initio calculations. [Fe@Ge10 ]4- and [Co@Ge10 ]3- have D5h -symmetric pentagonal prismatic structure and [Fe@Sn10 ]4- adopts the C2v -symmetric structure as their ground-state structures, whereas all the other clusters possess D4d bicapped square antiprismatic structures, in consistent with the experimental values when available. Natural bonding orbital and electron localization function disclosed that the negative charges are localized on the central atoms rather than the cages while the TME ionic bonding interactions increase in the order of Ge < Sn < Pb. The energy decomposition analysis revealed that the total bonding energy ∆Eint between central TM and E10 cage is above 150 kcal/mol. The ionic bonding interaction termed as electrostatic interaction ∆Eelstat increases in the order of Ge < Sn < Pb and becomes higher than the covalent bonding interactions termed as total orbital interactions ∆Eorb . Among the total orbital interactions, the π back donations from the TM-d orbitals to the empty cage orbitals consisting of E-p orbitals, the magnitude of which is importantly affected by the cage symmetry, are dominant contributions.

Layered Oxide Cathodes Promoted by Crystal Regulation Strategies for Potassium-Ion Batteries.

Layered oxide cathodes have demonstrated great potential for potassium-ion batteries (PIBs) on account of high reversible capacity, appropriate diffusion paths, and low cost. However, their electrochemical performance in PIBs is generally worse than that in lithium-ion batteries due to large structural changes and deformations during charging and discharging. To improve their potassium storage performance, a series of strategies have been developed in recent studies. In this review, we summarize the latest advancements in layered oxide cathodes for PIBs through different crystal regulation strategies, including transition metal layer doping, potassium content optimization, oxygen partial substitution, functional morphology construction and air stability improvement. Meanwhile, the relationship between the electrochemical properties and structural evolution of these modified cathodes is also investigated. In addition, the challenges and prospects of these layered oxide cathodes in PIBs are analyzed in detail, providing constructive insights for future applications of PIBs.

Dynamic Impedance Analysis of Intestinal Anastomosis during High-Frequency Electric Field Welding Process.

The success rate of the electrosurgical high-frequency electric field welding technique lies in reasonable control of the welding time. However, the final impedance value used to control the welding time varies due to differences in tissue size and the welding method during the welding process. This study aims to introduce a new reference indicator not limited by impedance size from dynamic impedance to achieve an adequate weld strength with minimal thermal damage, providing feedback on the tissue welding effect in medical power supplies. End-to-end anastomosis experiments were conducted with porcine small intestine tissue under seven levels of compression pressure. The dynamic impedance changes were analyzed, combined with compression pressure, temperature, moisture, and collagen during welding. The welding process was divided into three stages according to the dynamic impedance, with impedance decreasing in Period Ⅰ and impedance increasing in Period Ⅲ. Period Ⅲ was the key to high-strength connections due to water evaporation and collagen reorganization. The dynamic impedance ratio is defined as the final impedance divided by the minimum impedance, and successful welding would be predicted when detecting the dynamic impedance ratio over 4 (n = 70, p < 0.001). Dynamic impedance monitoring can be used as a macroscopic real-time prediction of the anastomosis effect.

Stable Noble Gas Compounds Based on Superelectrophilic Anions [B12 (BO)11 ]- and [B12 (OBO)11 ].

Superelectrophilic monoanions [B12 (BO)11 ]- and [B12 (OBO)11 ]- , generated from stable dianions [B12 (BO)12 ]2- and [B12 (OBO)12 ]2- , show great potential for binding with noble gases (Ngs). The binding energies, quantum theory of atoms in molecules (QTAIM), natural population analysis (NPA), energy decomposition analysis (EDA), and electron localization function (ELF) were carried out to understand the B-Ng bond in [B12 (BO)11 Ng]- and [B12 (OBO)11 Ng]- . The calculated results reveal that heavier noble gases (Ar, Kr, and Xe) bind covalently with both [B12 (BO)11 ]- and [B12 (OBO)11 ]- with large binding energies, making them potentially feasible to be synthesized. Only [B12 (OBO)11 ]- could form a covalent bond with helium or neon but the small binding energy of [B12 (OBO)11 He]- may pose a challenge for its experimental detection.

An ex vivo preliminary investigation into the impact of parameters on tissue welding strength in small intestine mucosa-mucosa end-to-end anastomosis.

Background: Tissue welding is an electrosurgical technique that can fuse tissue for small intestine anastomosis. However, limited knowledge exists on its application in mucosa-mucosa end-to-end anastomosis. This study investigates the effects of initial compression pressure, out-put power, and duration time on anastomosis strength ex vivo in mucosa-mucosa end-to-end anastomosis. Methods: Ex vivo porcine bowel segments were used to create 140 mucosa-mucosa end-to-end fusions. Different experimental parameters were employed for fusion, including initial com-pression pressure (50kPa-400 kPa), output power (90W, 110W, and 140W), and fusion time (5, 10, 15, 20 s). The fusion quality was measured by burst pressure and optical microscopes. Results: The best fusion quality was achieved with an initial compressive pressure between 200 and 250 kPa, an output power of 140W, and a fusion time of 15 s. However, an increase in output power and duration time resulted in a wider range of thermal damage. There was no significant difference between the burst pressure at 15 and 20 s (p > 0.05). However, a substantial increase in thermal damage was observed with longer fusion times of 15 and 20 s (p < 0.05). Conclusion: The best fusion quality for mucosa-mucosa end-to-end anastomosis ex vivo is achieved when the initial compressive pressure is between 200 and 250 kPa, the output power is approximately 140W, and the fusion time is approximately 15 s. These findings can serve as a valuable theoretical foundation and technical guidance for conducting animal experiments in vivo and subsequent tissue regeneration.

Risk factors for and prevention of caries and dental erosion in children and adolescents with asthma.

There are many studies and reviews of the relationship between the asthma disease in young individuals on the one hand and caries and dental erosion on the other. The causes of caries and dental erosion might be related to the asthmatic drugs, low pH and the sweeteners that the inhaled drug contains and perhaps even the lifestyle of children and adolescents with asthma. The main focus of this review is therefore to describe various preventive strategies, based on long experience of preventive dental care in Sweden. Two fact boxes are presented, one on fluoride toothpaste as a population-based intervention for different ages and one on diet counselling in children and adolescents with asthma. The most important thing is to introduce fluoride toothpaste early in the child's life and that the parents brush the child's teeth twice a day, in the morning after breakfast and at night before bedtime, up to the age of 10. Moreover, a high-risk approach with an additional fluoride supply at home is presented, together with the application of fluoride varnish at the clinic. Regarding diet counselling, it is important to make sure that the child has regular meals during the day, maximum five to six times a day, to allow the teeth to rest between meals and restrict sweets and soft drinks to once a week. It is important to identify children and adolescents with asthma as early as possible and to refer them to a dental team for preventive treatment.

Characteristics of Collagen Changes in Small Intestine Anastomoses Induced by High-Frequency Electric Field Welding.

High-frequency electric field welding-induced tissue fusion has been explored as an advanced surgical method for intestinal anastomoses; however, intrinsic mechanisms remain unclear. The aim of this study was to investigate microcosmic changes of collagen within the fusion area, with various parameters. Ex vivo small intestine was fused with mucosa-mucosa. Four levels of compressive pressure (100 kPa, 150 kPa, 200 kPa, 250 kPa) were applied for 10 s in order to fuse the colons under a power level of 140 W. Then, collagen fibers of the fusion area were examined by fibrillar collagen alignment and TEM. Three levels of power (90 W, 110 W, 140 W) and three levels of time (5 s, 10 s, 20 s) were applied in order to fuse colons at 250 kPa, and then collagen within the fusion area was examined by Raman spectroscopy. Fibrillar collagen alignment analysis showed that with the increase in compression pressure, alignment of the collagen in the fusion area gradually increased, and the arrangement of collagen fibers tended to be consistent, which was conducive to the adhesion of collagen fibers. TEM showed that pressure changed the distribution and morphology of collagen fibers. Raman spectroscopy showed that increased power and time within a certain range contributed to collagen cross linking. Peak positions of amide I band and amide III band changed. These results suggested that higher power and a longer amount of time resulted in a decrease in non-reducible cross links and an increase in reducible cross links. Compression pressure, power, and time can affect the state of collagen, but the mechanisms are different. Compressive pressure affected the state of collagen by changing its orientation; power and time denatured collagen by increasing temperature and improved the reducible cross linking of collagen to promote tissue fusion.

Confining ultrafine SnS nanoparticles in hollow multichannel carbon nanofibers for boosting potassium storage properties.

SnS has been extensively investigated as a potential anode material in potassium-ion batteries (PIBs) for its high theoretical capacity. Nonetheless, it suffers a limited cyclic lifespan owing to its poor electronic conductivity and huge volume expansion. This work proposed a facile approach where SnS nanocrystals are confined in the walls of hollow multichannel carbon nanofibers (denoted SnS@HMCFs) to tackle the issues above. In contrast to previous studies, impregnated ultrafine SnS nanocrystals in HMCFs compactly can increase the SnS loading number per unit area of the carbon matrix. Furthermore, the unique hollow multichannel carbon nanofibers are used as a robust carrier to uniformly distribute the SnS nanocrystals. This can significantly accelerate K+/electron transport, resulting in large specific capacity, outstanding rate performance, and steady cycling property for PIBs. High reversible capacities of 415.5 mAh g-1 at 0.1 A g-1 after 300 cycles and 245.5 mAh g-1 at 1 A g-1 after 1000 cycles are retained, suggesting great potential of SnS@HMCFs as a negative electrode material for PIBs. Additionally, when the SnS@HMCF anode is assembled with the KVPO4F cathode, the obtained full cell shows a large discharge capacity of 165.3 mAh g-1 after 200 cycles at 0.1 A g-1.

Implantation of Fe7S8 nanocrystals into hollow carbon nanospheres for efficient potassium storage.

As a desirable candidate for lithium-ion batteries, potassium-ion batteries (PIBs) have aroused great interest because of their low cost and high power and energy densities. However, the insertion/extraction of K+ with a large radius (1.38 Å) usually bring about the destruction of the electrode materials. Here, ultrafine Fe7S8 nanocrystals are successfully implanted into hollow carbon nanospheres (Fe7S8@HCSs) via a facile solvothermal method and subsequent novel low-temperature sulfurization, which avoid the aggregation of Fe7S8 nanoparticles produced during high-temperature sulfidation. The ultrafine Fe7S8 nanoparticles and hollow carbon spheres can not only buffer the severe expansion/shrinkage of electrode materials caused by the repeated insertion/extraction of K+, but also provide additional accessible pathways for the high-rate K+ transmission. When tested as an anode material for PIBs, Fe7S8@HCSs achieve impressive K+ storage capacity of 523.2 mAh g-1 at 0.1 A g-1 after 100 cycles and remarkable rate capacity of 176.3 mAh g-1 at 5 A g-1. Further, assembling this anode with a K2NiFe(CN)6 cathode yields stable cycling performance, revealing its great potential for large-scale energy storage applications.

Scalable synthesis of Na2MVF7 (M = Mn, Fe, and Co) as high-performance cathode materials for sodium-ion batteries.

We demonstrate an economical polytetrafluoroethylene-assisted fluorination method to synthesize three binary sodium-rich fluorides Na2MVF7 (M = Mn, Fe, and Co). The optimal Na2FeVF7 cathode delivers a high reversible capacity of 146.5 mA h g-1 based on active Fe2+/Fe3+ and V3+/V4+ redox reactions in sodium-ion batteries. A steady cycling performance with a high capacity retention of 95% over 200 cycles is achieved owing to the negligible structural change during Na+ insertion/extraction.