Electrospun TiO2 Nanofibers Featuring Surface Oxygen Vacancies as a Multifunctional Interlayer for High-Performance Lithium-Sulfur Batteries in a Wide Temperature Range.

Despite great achievements having been made in lithium-sulfur batteries (LSBs), further improvements regarding rate performance, cycle life, and operating temperature are needed for realistic applications. Herein, we developed a simple electrospun method for the preparation of TiO2 coaxial nanofiber (TCNFs)-modified Celgard separators to suppress the polysulfide shuttling. LSBs with a TCNF/Celgard separator display excellent electrochemical performance. For an areal sulfur loading of 2.5 mg cm-2, the cells exhibited a capacity of 1279 mA h g-1 at 0.5 A g-1, remained 798 mA h g-1 at 2.5 A g-1, and low-capacity decay of 0.057% per cycle within 1000 cycles. At 50 and -10 °C, the capacity of the cells is maintained at 932 and 931 mA h g-1 after 80 cycles at 0.5 A g-1, respectively. Detailed structural analysis and theoretical calculations revealed that the hollow-structured TCNFs offer high density of accessible electropositive Ti sites and oxygen vacancies and thus enables efficient trapping of polysulfides and facilitates Li+ transfer, leading to excellent performance. The simplicity of this strategy and the diversity of hollow-structured metal oxides holds great promise to design separators for high-performance LSBs.

Enhanced Catalytic Activity of TEMPO-Mediated Aerobic Oxidation of Alcohols via Redox-Active Metal-Organic Framework Nodes.

Metal-organic frameworks (MOFs) are outstanding platforms for heterogeneous catalysis due to their tunable pore size, huge surface area, large porosity, and potential active sites. The design and synthesis of MOF/organocatalyst co-catalytic systems have attracted considerable interest owing to their high catalytic activity, low toxicity, and mild reaction conditions. Herein, we reported the synthesis of a bifunctional TEMPO-IsoNTA organocatalyst featuring a pyridyl group as an anchoring site and a TEMPO radical as a catalytic active site. By using the topologically isomorphic structures of MIL-101(Fe) and MIL-101(Cr) as co-catalysts, these MOF/TEMPO-IsoNTA systems enable the efficient aerobic oxidation of various alcohols to their corresponding aldehydes or ketones under mild conditions. Notably, the MIL-101(Fe)/TEMPO-IsoNTA system exhibits superior catalytic activity, thanks to their redox-active FeIII-oxo nodes, which facilitate the regeneration of TEMPO-IsoNTA. Our research not only solves the problem of potential heavy metal contamination in the TEMPO-based homogeneous catalytic system, but also enriches the understanding of synergism of MOFs/organocatalysts.

Metal-Organic Frameworks Functionalized Separators for Lithium-Sulfur Batteries.

Lithium sulfur batteries (LSBs) have attracted tremendous attention owing to their high theoretical specific capacity and specific energy. However, their practical applications are hindered by poor cyclic life, mainly caused by polysulfide shuttling. The development of advanced materials to mitigate the polysulfide shuttling effect is urgently demanded. Metal-organic frameworks (MOFs) have been exploited as multifunctional materials for the decoration of separators owing to their high surface area, structural diversity, tunable pore size, and easy tailor ability. In this review, we aim to present the state-of-the-art MOF-based separators for LSBs. Particular attention is paid to the rational design (pore aperture, metal node, functionality, and dimension) of MOFs with enhanced ability for anchoring polysulfides and facilitating Li+ transportation. Finally, the challenges and perspectives are provided regarding to the future design MOF-based separators for high-performance LSBs.

Liquid-Phase Epitaxial Growth of Highly Oriented and Multivariate Surface-Attached Metal-Organic Frameworks.

Multivariate metal-organic frameworks (MTV-MOFs) incorporating multiple chemical functionalities within single-phase crystalline materials show superior properties that arise from synergistic effects. Herein, we report an efficient and versatile method for the growth of highly oriented multivariate surface-attached MOFs (MTV-SURMOFs) by the combination of the liquid-epitaxial growth method (LPE) and the mixed-linker strategy. Twenty-six MTV-SURMOFs of the [M2L2P] type with a maximum of five different dicarboxylate linkers (L) were deposited onto suitably functionalized surfaces. Systematic studies by infrared reflection absorption (IRRA) spectroscopy and surface XRD provide evidence for the formation of highly oriented MTV-SURMOFs. Interestingly, the pKa's of the dicarboxylate linkers play a crucial role for the orientational quality of the MTV-SURMOFs. In addition, benzene uptake experiments showed that the MTV-SURMOFs exhibit up to 2.6 times higher adsorption capacity as compared to the single-linker SURMOFs, demonstrating the synergistic effects in these surface systems.

[Effect of LLLI on Secretion of ALP and Intracellular Calcium Concentration in Osteoblasts under Mechanical Stress].

In order to reveal the mechanism of LLLI accelerating teeth moving, we investigated the changes of alkaline phosphatase and intracellular calcium concentration when osteoblasts under stress were subjected low-level-laser-irradiation (LLLI). MG-63 cells were divided into four groups: control group, stress group, LLLI group and LLLI-stress group. Osteoblasts were subjected to the mechanical stress by a four-point bending system at 0.5 Hz and 3 000 µstrain. The secretions of ALP of each group are measured by spectrophotometer. In the second part, MG-63 cells were divided into two groups: stress group and LLLI-stress group. We checked intracellular calcium concentration via FCM and fluorescent indicator fluo-3/AM at 0, 5, 15, 30 and 60 min under stress. LLLI- stress group will receive LLLI for 1 min after stress. Compared to a control group, increased ALP secretions were observed in the other three groups. But ALP secretions in LLLI-stress group were lower than stress group and LLLI group. THE changing curve of intracellular calcium concentration in laser-stress groups is gentle instead of "jumping" in stress group. Proper stress, LLLI and combined application of these two can increase the secretions of ALP in osteoblasts compared to the control group. But the secretions of ALP decreased when combined application of stress and LLLI compared to using alone. LLLI can regulate the changing rhythm of concentration of the intracellular calcium to promote proliferation of MG-63 cell under stress, which means LLLI can reduce the bone-formation of osteoblasts under stress.

Minimization of Surface Energies and Ripening Outcompete Template Effects in the Surface Growth of Metal-Organic Frameworks.

As well-oriented, surface-bound metal-organic frameworks become the centerpiece of many new applications, a profound understanding of their growth mode becomes necessary. This work shows that the currently favored model of surface templating is in fact a special case valid only for systems with a more or less cubic crystal shape, while in less symmetric systems crystal ripening and minimization of surface energies dominate the growth process.

Insight into the Oriented Growth of Surface-Attached Metal-Organic Frameworks: Surface Functionality, Deposition Temperature, and First Layer Order.

The layer-by-layer growth of a surface-attached metal-organic framework (SURMOF), [Cu2(F4bdc)2(dabco)] (F4bdc = tetrafluorobenzene-1,4-dicarboxylate and dabco = 1,4-diazabicyclo-[2.2.2]octane), on carboxylate- and pyridine-terminated surfaces has been investigated by various surface characterization techniques. Particular attention was paid to the dependency of the crystal orientation and morphology on surface functionality, deposition temperature, and first layer order. For the fully oriented deposition of SURMOFs, not only a suitable surface chemistry but also the appropriate temperature has to be chosen. In the case of carboxylate-terminated surfaces, the expected [100] oriented [Cu2(F4bdc)2(dabco)] SURMOF can be achieved at low temperatures (5 °C). In contrast, the predicted [001] oriented SURMOF on pyridine-terminated surface was obtained only at high deposition temperatures (60 °C). Interestingly, we found that rearrangement processes in the very first layer determine the final orientation (distribution) of the growing crystals. These effects could be explained by a surprisingly hampered substitution at the apical position of the Cu2-paddle wheel units, which requires significant thermal activation, as supported by quantum-chemical calculations.

Two-Dimensional Metal-Organic Framework Nanosheets: Synthesis and Applications in Electrocatalysis and Photocatalysis.

Two-dimensional metal-organic nanosheets (2D MONs) are an emerging class of ultrathin, porous, and crystalline materials. The organic/inorganic hybrid nature offers MONs distinct advantages over other inorganic nanosheets in terms of diversity of organic ligands and metal notes. Compared to bulk three-dimensional metal-organic frameworks, 2D MONs possess merits of high density and readily accessible catalytic sites, reduced diffusion pathways for reactants/products, and fast electron transport. These features endow MONs with enhanced physical/chemical properties and are ideal for heterogeneous catalysis. In this Review, state-of-the-art synthetic methods for the fabrication of 2D MONs were summarized. The advances of 2D MONs-based materials for electrocatalysis and photocatalysis, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2 RR), and electro-/photocatalytic organic transformations were systematically discussed. Finally, the challenges and perspectives regarding future design and synthesis of 2D MONs for high-performance electrocatalysis and photocatalysis were provided.

Electrochemical Synthesis of Benzimidazoles via Dehydrogenative Cyclization of Amidines.

The development of efficient and sustainable methodologies for the synthesis of N-heterocycles is a constant focus of organic synthesis. Herein an electrochemical method is reported for the synthesis of benzimidazoles through dehydrogenative cyclization of easily available N-aryl amidines. The reactions were conducted under simple constant current conditions in an undivided cell without need for catalysts, chemical oxidants, or additives, and produced H2 as the only theoretical byproduct.

Synthesis of TEMPO radical decorated hollow porous aromatic frameworks for selective oxidation of alcohols.

A bottom-up approach was developed to prepare TEMPO radical decorated hollow aromatic frameworks (HPAF-TEMPO) by using TEMPO radical functionalized monomers and SiO2 nanospheres as templates. The accessible inner layer, high density of TEMPO sites, and hybrid micro-/mesopores of the HPAF-TEMPO enable the aerobic oxidation of a broad range of alcohols with high efficiency and excellent selectivity.

Effects of simvastatin on relapse and remodeling of periodontal tissues after tooth movement in rats.

INTRODUCTION: Our objectives were to determine the effects of simvastatin on relapse and periodontal tissue remodeling after experimental tooth movement in rats and to explore the molecule mechanism. METHODS: Thirty-two adult male Wistar rats were randomly divided into 2 groups. Bilateral mandibular first molars were moved mesially with nickel-titanium closed-coil springs in both groups. On the 21st day, the springs were removed, and dental casts were made. Animals in the experimental group began receiving simvastatin at a dose of 2.5 mg per kilogram per day for 4 weeks, and animals in the control group received 0.9% sodium chloride. The results were evaluated by model measuring and immunohistochemistry staining. RESULTS: Relapse distances and relapse percentages were decreased in the simvastatin group compared with the controls. Osteoprotegerin expression increased, and RANKL decreased. CONCLUSIONS: These results indicate that simvastatin inhibits the bone-resorbing activity of osteoclasts while stimulating bone formation, probably by controlling the ratio of local osteoprotegerin to RANKL in the periodontal tissues. Therefore, it might be useful for retention.

Sema6A-plexin-A2 axis stimulates RANKL-induced osteoclastogenesis through PLCγ-mediated NFATc1 activation.

Recently, several plexins and semaphorins have been associated with osteoclastogenesis, a vital process for bone remodeling. Plexin-A2 is implicated in bone homeostasis, however, whether it plays a role in osteoclastogenesis and the underlying mechanism remain unknown. We show that plexin-A2 expression is upregulated during RANKL-induced osteoclastogenesis. In addition, the soluble Sema6A fused with IgG1 Fc region (Fc-Sema6A) interacts with plexin-A2 from cell lysates of osteoclasts, suggesting that plexin-A2 acts as a receptor of Sema6A in osteoclasts. Moreover, Sema6A treatment stimulates RANKL-induced osteoclastogenesis, and this effect is abolished when plexin-A2 is neutralized, which illustrates an indispensable role of plexin-A2 in mediating Sema6A effect on osteoclastogenesis. Mechanistically, Sema6A-plexin-A2 axis enhances RANKL-induced activation of PLCγ as well as downstream target NFATc1, one master transcriptional factor of osteoclastogenesis. Lastly, inhibition of PLCγ by pharmacological inhibitor U73122 abrogates Sema6A-stimulated NFATc1 activation and RANKL-induced osteoclastogenesis, thus demonstrating that the PLCγ-mediated NFATc1 activation accounts for the promotive role of Sema6A-plexin-A2 axis in RANKL-induced osteoclastogenesis. Taken together, this study uncovers a novel role of Sema6A and plexin-A2 in osteoclastogenesis, and also offers them as possible therapeutic targets in the intervention of osteolytic diseases.

Zr-Metal-Organic Frameworks Featuring TEMPO Radicals: Synergistic Effect between TEMPO and Hydrophilic Zr-Node Defects Boosting Aerobic Oxidation of Alcohols.

Metal-organic frameworks (MOFs) featuring multiple catalytic units are excellent platforms for heterogeneous catalysis. However, the synergism between multiple catalytic units for catalysis is far from being well understood. Herein, we reported the synthesis of a robust 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) radical-functionalized Zr-MOF (UiO-68-TEMPO) in the form of single-crystalline and microsized crystals with varied missing linker defects. Detailed catalytic studies and theoretical calculations reveal that the synergistic effect between the TEMPO radicals and hydrophilic and defective Zr-nodes endows UiO-68-TEMPO with superior catalytic activity toward aerobic oxidation of alcohols. Our work not only offers a new route to design and synthesize highly effective MOF catalysts but also provides insights into the synergism between multiple catalytic sites.

Side-Group Effect on Electron Transport of Single Molecular Junctions.

In this article, we have investigated the influence of the nitro side-group on the single molecular conductance of pyridine-based molecules by scanning tunneling microscopy break junction. Single molecular conductance of 4,4'-bipyridine (BPY), 3-nitro-4-(pyridin-4-yl)pyridine (BPY-N), and 3-nitro-4-(3-nitropyridin-4-yl)pyridine (BPY-2N) were measured by contact with Au electrodes. For the BPY molecular junction, two sets of conductance were found with values around 10-3.1 G0 (high G) and 10-3.7 G0 (low G). The addition of nitro side-group(s) onto the pyridine ring resulted in lower conductance of 10-3.8 G0 for BPY-N and 10-3.9 G0 for BPY-2N, respectively, which can be attributed to the twist angle of two pyridine rings. Moreover, the steric hindrance of nitro group(s) also affects the contacting configuration of electrode-molecule-electrode. As a consequence, only one set of conductance value was observed for BPY-N and BPY-2N. Our work clearly shows the important role of side-groups on the electron transport of single-molecule junctions.

Patterned deposition of metal-organic frameworks onto plastic, paper, and textile substrates by inkjet printing of a precursor solution.

Flexible in many aspects: inkjet printing of metal-organic frameworks permits their larger area, high-resolution deposition in any desired pattern, even in the form of gradients or shades. When flexible substrates are used, many applications can be envisioned, such as sensing and capture of hazardous gases for personal safety measures.

The oriented and patterned growth of fluorescent metal-organic frameworks onto functionalized surfaces.

A metal-organic framework (MOF) material, [Zn(2)(adc)(2)(dabco)] (adc = anthracene-9,10-dicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]-octane), the fluorescence of which depends on the loading of its nanopores, was synthesized in two forms: as free-flowing nanocrystals with different shapes and as surface-attached MOFs (SURMOFs). For the latter, we used self-assembled monolayers (SAMs) bearing functional groups, such as carboxylate and pyridyl groups, capable of coordinating to the constituents of the MOF. It could be demonstrated that this directed coordination also orients the nanocrystals deposited at the surface. Using two different patterning methods, i.e., microcontact printing and electron-beam lithography, the lateral distribution of the functional groups could be determined in such a way that the highly localized deposition of the SURMOF films became possible.