14-Electron Redox Chemistry Enabled by Salen-Based π-Conjugated Framework Polymer Boosting High-Performance Lithium-Ion Storage.

A paucity of redox centers, poor charge transport properties, and low structural stability of organic materials obstruct their use in practical applications. Herein, these issues have been addressed through the use of a redox-active salen-based framework polymer (RSFP) containing multiple redox-active centers in π-conjugated configuration for applications in lithium-ion batteries (LIBs). Based on its unique architecture, RSFP exhibits a superior reversible capacity of 671.8 mAh g-1 at 0.05 A g-1 after 168 charge-discharge cycles. Importantly, the lithiation/de-lithiation performance is enhanced during operation, leading to an unprecedented reversible capacity of 946.2 mAh g-1 after 3500 cycles at 2 A g-1. The structural evolution of RSFP is studied ex situ using X-ray photoelectron spectroscopy, revealing multiple active C═N, C─O, and C═O sites and aromatic sites such as benzene rings. Remarkably, the emergence of C═O originated from C─O is triggered by an electrochemical process, which is beneficial for improving reversible lithiation/delithiation behavior. Furthermore, the respective strong and weak binding interactions between redox centers and lithium ions, corresponding to theoretical capacities of 670.1 and 938.2 mAh g-1, have been identified by density functional theory calculations manifesting 14-electron redox reactions. This work sheds new light on routes for the development of redox-active organic materials for energy storage applications.

Synthesis of millimeter-scale ZIF-8 single crystals and their reversible crystal structure changes.

Among various metal-organic frameworks (MOFs), the zeolitic imidazole framework (ZIF), constructed by the regular arrangement of 2-methylimidazole and metal ions, has garnered significant attention due to its distinctive crystals and pore structures. Variations in the sizes and shapes of ZIF crystals have been reported by changing the synthesis parameters, such as the molar ratios of organic ligands to metal ions, choice of solvents, and temperatures. Nonetheless, the giant ZIF-8 single crystals beyond the typical range have rarely been reported. Herein, we present the synthesis of millimeter-scale single crystal ZIF-8 using the solvothermal method in N,N-diethylformamide. The resulting 1-mm single crystal is carefully characterized through N2 adsorption-desorption isotherms, scanning electron microscopy, and other analytical techniques. Additionally, single-crystal X-ray diffraction is employed to comprehensively investigate the framework's mobility at various temperatures.

Millimeter-sized ZIF-8 single crystals were synthesized using the solvothermal method. These crystals exhibit a notable BET surface area of 1681 m²âˆ™g⁻¹ and demonstrate a reversible change in their crystal structure.

Involvement of Degenerating 21.5 kDa Isoform of Myelin Basic Protein in the Pathogenesis of the Relapse in Murine Relapsing-Remitting Experimental Autoimmune Encephalomyelitis and MS Autopsied Brain.

Multiple sclerosis (MS) is the chronic inflammatory demyelinating disease of the CNS. Relapsing-remitting MS (RRMS) is the most common type of MS. However, the mechanisms of relapse and remission in MS have not been fully understood. While SJL mice immunized with proteolipid protein (PLP) develop relapsing-remitting experimental autoimmune encephalomyelitis (RR-EAE), we have recently observed that some of these mice were resistant to the active induction of relapsing EAE after initial clinical and histological symptoms of EAE with a severity similar to the relapsing EAE mice. To clarify the mechanism of relapsing, we examined myelin morphology during PLP139-151-induced RR-EAE in the SJL mice. While RR-EAE mice showed an increased EAE severity (relapse) with CNS inflammation, demyelination with abnormal myelin morphology in the spinal cord, the resistant mice exhibited a milder EAE phenotype with diminished relapse. Compared with the RR-EAE mice, the resistant mice showed less CNS inflammation, demyelination, and abnormalities of the myelin structure. In addition, scanning electron microscopic (SEM) analysis with the osmium-maceration method displayed ultrastructural abnormalities of the myelin structure in the white matter of the RR-EAE spinal cord, but not in that of the resistant mice. While the intensity of myelin staining was reduced in the relapsing EAE spinal cord, immunohistochemistry and immunoblot analysis revealed that the 21.5 kDa isoform of degenerating myelin basic protein (MBP) was specifically induced in the relapsing EAE spinal cord. Taken together, the neuroinflammation-induced degenerating 21 kDa isoform of MBP sheds light on the development of abnormal myelin on the relapse of MS pathogenesis.

Tailoring the Surface and Interface Structures of Copper-Based Catalysts for Electrochemical Reduction of CO2 to Ethylene and Ethanol.

Electrochemical CO2 reduction to valuable ethylene and ethanol offers a promising strategy to lower CO2 emissions while storing renewable electricity. Cu-based catalysts have shown the potential for CO2 -to-ethylene/ethanol conversion, but still suffer from low activity and selectivity. Herein, the effects of surface and interface structures in Cu-based catalysts for CO2 -to-ethylene/ethanol production are systematically discussed. Both reactions involve three crucial steps: formation of CO intermediate, CC coupling, and hydrodeoxygenation of C2 intermediates. For ethylene, the key step is CC coupling, which can be enhanced by tailoring the surface structures of catalyst such as step sites on facets, Cu0 /Cuδ+ species and nanopores, as well as the optimized molecule-catalyst and electrolyte-catalyst interfaces further promoting the higher ethylene production. While the controllable hydrodeoxygenation of C2 intermediate is important for ethanol, which can be achieved by tuning the stability of oxygenate intermediates through the metallic cluster induced special atomic configuration and bimetallic synergy induced the double active sites on catalyst surface. Additionally, constraining CO coverage by the complex-catalyst interface and stabilizing CO bond by N-doped carbon/Cu interface can also enhance the ethanol selectivity. The structure-performance relationships will provide the guidance for the design of Cu-based catalysts for highly efficient reduction of CO2 .

Ti3+ Tuning the Ratio of Cu+ /Cu0 in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction.

Hydrogenation of diesters to diols is a vital process for chemical industry. The inexpensive Cu+ /Cu0 -based catalysts are highly active for the hydrogenation of esters, however, how to efficiently tune the ratio of Cu+ /Cu0 and stabilize the Cu+ is a great challenge. In this work, it is demonstrated that doped Ti ions can tune the ratio of Cu+ /Cu0 and stabilize the Cu+ by the TiOCu bonds in Ti-doped SiO2 supported Cu nanoparticle (Cu/Ti-SiO2 ) catalysts for the high conversion of dimethyl adipate to 1,6-hexanediol. In the synthesis of the catalysts, the Ti4+ OCu2+ bonds promote the reduction of Cu2+ to Cu+ by forming Ti3+ OV Cu+ (OV : oxygen vacancy) bonds and the amount of Ti doping can tune the ratio of Cu+ /Cu0 . In the catalytic reaction, the O vacancy activates CO in the ester by forming new Ti3+ δ OR Cu1+ δ bonds (OR : reactant oxygen), and Cu0 activates hydrogen. After the products are desorbed, the Ti3+ δ OR Cu1+ δ bonds return to the initial state of Ti3+ OV Cu+ bonds. The reversible TiOCu bonds greatly improve the activity and stability of the Cu/Ti-SiO2 catalysts. When the content of Ti is controlled at 0.4 wt%, the conversion and selectivity can reach 100% and 98.8%, respectively, and remain stable for 260 h without performance degradation.

Spherical Superstructure of Boron Nitride Nanosheets Derived from Boron-Containing Metal-Organic Frameworks.

The assembly of two-dimensional (2D) nanosheets into three-dimensional (3D) well-organized superstructures is one of the key topics in materials chemistry and physics, due to their potential applications in various fields. Herein, starting from the crystalline metal-organic framework (MOF) particles, a spherical superstructure consisting of metal-organic framework nanosheets (SS-MOFNSs) is synthesized via a simple solvothermal transformation process. After pyrolysis and nitrogenization in ammonia, the SS-MOFNSs are further transformed into the spherical superstructure consisting of boron nitride nanosheets (SS-BNNSs), which preserve the original spherical superstructure morphology. Taking advantage of this unique superstructure, the resulting SS-BNNSs exhibit excellent catalytic activity for selective oxidative dehydrogenation of propane to produce propylene and ethylene. The results of this work provide a novel synthetic strategy to fabricate 3D spherical superstructures consisting of 2D nanosheets for high-performance applications in catalysis, energy storage, as well as other related fields.

Mesoporous Metal-Metalloid Amorphous Alloys: The First Synthesis of Open 3D Mesoporous Ni-B Amorphous Alloy Spheres via a Dual Chemical Reduction Method.

Selective hydrogenation of nitriles is an industrially relevant synthetic route for the preparation of primary amines. Amorphous metal-boron alloys have a tunable, glass-like structure that generates a high concentration of unsaturated metal surface atoms that serve as active sites in hydrogenation reactions. Here, a method to create nanoparticles composed of mesoporous 3D networks of amorphous nickel-boron (Ni-B) alloy is reported. The hydrogenation of benzyl cyanide to ß-phenylethylamine is used as a model reaction to assess catalytic performance. The mesoporous Ni-B alloy spheres have a turnover frequency value of 11.6 h-1 , which outperforms non-porous Ni-B spheres with the same composition. The bottom-up synthesis of mesoporous transition metal-metalloid alloys expands the possible reactions that these metal architectures can perform while simultaneously incorporating more Earth-abundant catalysts.

Designed Patterning of Mesoporous Metal Films Based on Electrochemical Micelle Assembly Combined with Lithographical Techniques.

Mesoporous noble metals and their patterning techniques for obtaining unique patterned structures are highly attractive for electrocatalysis, photocatalysis, and optoelectronics device applications owing to their expedient properties such as high level of exposed active locations, cascade electrocatalytic sites, and large surface area. However, patterning techniques for mesoporous substrates are still limited to metal oxide and silica films, although there is growing demand for developing techniques related to patterning mesoporous metals. In this study, the first demonstration of mesoporous metal films on patterned gold (Au) substrates, prefabricated using photolithographic techniques, is reported. First, different growth rates of mesoporous Au metal films on patterned Au substrates are demonstrated by varying deposition times and voltages. In addition, mesoporous Au films are also fabricated on various patterns of Au substrates including stripe and mesh lines. An alternative fabrication method using a photoresist insulating mask also yields growth of mesoporous Au within the patterning. Moreover, patterned mesoporous films of palladium (Pd) and palladium-copper alloy (PdCu) are demonstrated on the same types of substrates to show versatility of this method. Patterned mesoporous Au films (PMGFs) show higher electrochemically active surface area (ECSA) and higher sensitivity toward glucose oxidation than nonpatterned mesoporous Au films (NMGF).

Rational Design of Nanoporous MoS2 /VS2 Heteroarchitecture for Ultrahigh Performance Ammonia Sensors.

2D transition metal dichalcogenides (TMDs) have received widespread interest by virtue of their excellent electrical, optical, and electrochemical characteristics. Recent studies on TMDs have revealed their versatile utilization as electrocatalysts, supercapacitors, battery materials, and sensors, etc. In this study, MoS2 nanosheets are successfully assembled on the porous VS2 (P-VS2 ) scaffold to form a MoS2 /VS2 heterostructure. Their gas-sensing features, such as sensitivity and selectivity, are investigated by using a quartz crystal microbalance (QCM) technique. The QCM results and density functional theory (DFT) calculations reveal the impressive affinity of the MoS2 /VS2 heterostructure sensor toward ammonia with a higher adsorption uptake than the pristine MoS2 or P-VS2 sensor. Furthermore, the adsorption kinetics of the MoS2 /VS2 heterostructure sensor toward ammonia follow the pseudo-first-order kinetics model. The excellent sensing features of the MoS2 /VS2 heterostructure render it attractive for high-performance ammonia sensors in diverse applications.

Superparamagnetic nanoarchitectures for disease-specific biomarker detection.

The detection of clinically relevant disease-specific biomolecules, including nucleic acids, circulating tumor cells, proteins, antibodies, and extracellular vesicles, has been indispensable to understand their functions in disease diagnosis and prognosis. Therefore, a biosensor for the robust, ultrasensitive, and selective detection of these low-abundant biomolecules in body fluids (blood, urine, and saliva) is emerging in current clinical research. In recent years, nanomaterials, especially superparamagnetic nanomaterials, have played essential roles in biosensing due to their intrinsic magnetic, electrochemical, and optical properties. However, engineered multicomponent magnetic nanoparticle-based current biosensors that offer the advantages of excellent stability in a complex biomatrix; easy and alterable biorecognition of ligands, antibodies, and receptor molecules; and unified point-of-care integration have yet to be achieved. This review introduces the recent advances in superparamagnetic nanostructures for electrochemical and optical biosensing for disease-specific biomarkers. This review emphasizes the synthesis, biofunctionalization, and intrinsic properties of nanomaterials essential for robust, ultrasensitive biosensing. With a particular emphasis on nanostructure-based electrochemical and optical detection of disease-specific biomarkers such as nucleic acids (DNA and RNA), proteins, autoantibodies, and cells, this review also chronicles the needs and challenges of nanoarchitecture-based detection. These summaries provide further insights for researchers to inspire their future work on the development of nanostructures for integrating into biosensing and devices for a broad field of applications in analytical sensing and in clinic.

Intrinsic and Defect-Related Elastic Moduli of Boron Nitride Nanotubes As Revealed by in Situ Transmission Electron Microscopy.

Boron nitride nanotubes (BNNTs) are promising for mechanical applications owing to the high modulus, high strength, and inert chemical nature. However, up to now, precise evaluation of their elastic properties and their relation to defects have not been experimentally established. Herein, the intrinsic elastic modulus of BNNTs and its dependence on intrinsic and deliberately irradiation-induced extrinsic defects have been studied via an electric-field-induced high-order resonance technique inside a high-resolution transmission electron microscope (HRTEM). Resonances up to fourth order for normal modes and third order for parametric modes have been initiated in the cantilevered tubes, and the recorded frequencies are well consistent with the theoretical calculations with a discrepancy of ∼1%. The elastic moduli of the BNNTs measured from high-order resonance is about 906.2 GPa on average, with a standard deviation of 9.3%, which is found to be closely related to the intrinsic defect as cavities in the nanotube walls. Furthermore, electron irradiation in HRTEM has been used to study the effects of defects to elastic moduli and to evaluate the radiation resistance of the BNNTs. Along with an increase in the irradiation dose, the outer diameter has linearly reduced due to the knock-on effects. A defective shell with nearly constant thickness has been formed on the outer surface, and as a result, the elastic modulus decreases gradually to ∼662.9 GPa, which is still 3 times that of steel. Excellent intrinsic elastic properties and decent radiation-resistance prove that BNNTs could be a material of choice for applications in extreme environments, such as those existing in space.

Large-Scale Synthesis of MOF-Derived Superporous Carbon Aerogels with Extraordinary Adsorption Capacity for Organic Solvents.

Carbon aerogels (CAs) with 3D interconnected networks hold promise for application in areas such as pollutant treatment, energy storage, and electrocatalysis. In spite of this, it remains challenging to synthesize high-performance CAs on a large scale in a simple and sustainable manner. We report an eco-friendly method for the scalable synthesis of ultralight and superporous CAs by using cheap and widely available agarose (AG) biomass as the carbon precursor. Zeolitic imidazolate framework-8 (ZIF-8) with high porosity is introduced into the AG aerogels to increase the specific surface area and enable heteroatom doping. After pyrolysis under inert atmosphere, the ZIF-8/AG-derived nitrogen-doped CAs show a highly interconnected porous mazelike structure with a low density of 24 mg cm-3 , a high specific surface area of 516 m2 g-1 , and a large pore volume of 0.58 cm-3 g-1 . The resulting CAs exhibit significant potential for application in the adsorption of organic pollutants.

Chemical Design of Palladium-Based Nanoarchitectures for Catalytic Applications.

Palladium (Pd) plays an important role in numerous catalytic reactions, such as methanol and ethanol oxidation, oxygen reduction, hydrogenation, coupling reactions, and carbon monoxide oxidation. Creating Pd-based nanoarchitectures with increased active surface sites, higher density of low-coordinated atoms, and maximized surface coverage for the reactants is important. To address the limitations of pure Pd, various Pd-based nanoarchitectures, including alloys, intermetallics, and supported Pd nanomaterials, have been fabricated by combining Pd with other elements with similar or higher catalytic activity for many catalytic reactions. Herein, recent advances in the preparation of Pd-based nanoarchitectures through solution-phase chemical reduction and electrochemical deposition methods are summarized. Finally, the trend and future outlook in the development of Pd nanocatalysts toward practical catalytic applications are discussed.

Impaired social discrimination behavior despite normal social approach by kallikrein-related peptidase 8 knockout mouse.

For social mammals, recognition of conspecifics and discrimination of each other (social memory) is crucial to living in a stable colony. Here, we investigated whether kallikrein-related peptidase 8 (KLK8)-neuregulin 1 (NRG1)-ErbB signaling is crucial for social discrimination behavior using the social discrimination three chamber behavioral test. Klk8 knockout mice (NRG1-deactivated mice) exhibited normal social approach but impaired social discrimination. Intraventricular injection of recombinant NRG1177-246 into Klk8 knockout mice reversed this impaired social discrimination. This study reveals that KLK8 is a key regulator of NRG1-ErbB signaling, which contributes to social discrimination behavior.

Development of Sulfonic-Acid-Functionalized Mesoporous Materials: Synthesis and Catalytic Applications.

Sulfonic acid based mesostructures (SAMs) have been developed in recent years and have important catalytic applications. The primary applications of these materials are in various organic synthesis reactions, such as multicomponent reactions, carbon-carbon bond couplings, protection reactions, and Fries and Beckman rearrangements. This review aims to provide an overview of the recent developments in the field of SAMs with a particular emphasis on the reaction scope and advantages of heterogeneous solid acid catalysts.

Conversion of a 2D Lepidocrocite-Type Layered Titanate into Its 1D Nanowire Form with Enhancement of Cation Exchange and Photocatalytic Performance.

Layered titanates with one-dimensional (1D) shapes have been an important class of nanomaterials due to their combination of 1D and 2D fascinating properties. Among many layered titanates, lepidocrocite-type layered titanates have significant advantages such as superior intercalation and exfoliation properties, while the synthesis of the 1D-shape forms is still challenging. Here, we report on a facile one-pot hydrothermal conversion of a lepidocrocite-type layered titanate into the corresponding nanowire-shape form. The reaction mechanism involves the decomposition of the starting layered titanate into 1D small segments which assemble into the nanowire. This new nanowire shows properties resulting from the combination of 1D and 2D nanostructural features, excellent cation exchange ability, and high photoinduced charge separation and photocatalytic efficiency. As a demonstration, we evaluate the nanowire as a sequestrating material capable of collecting toxic cations, like Cd2+, from water and photoreducing them (immobilizing them tightly). We find that the nanowire shows an efficient and ultrafast photoimmobilization activity, whereas the starting layered titanate and a benchmark TiO2 photocatalyst (P25) show no activity under the identical conditions. The photoimmobilization rate (within 1 min) is considerably faster than the cation exchange rates reported for state-of-the-art cation exchangers (with no photoimmobilization ability). The nanowire used for photoimmobilization reactions is easily recovered from water by decantation, showing the possible practical use for safe disposal of toxic cations in the environment.

Roads to Formation of Normal Myelin Structure and Pathological Myelin Structure.

Demyelination and axonal damage are responsible for neurological deficits in demyelinating diseases including multiple sclerosis (MS), an inflammatory demyelinating disease of the central nervous system. However, the pathology of demyelination and axonal damage in MS is not fully understood. While immunologists have accumulated evidence, which is involved in many immunological events in these diseases, neuroscientists and anatomists have also investigated morphological changes of myelin in these diseases. In this chapter, a new concept of demyelination will be described.

Kallikrein 6 secreted by oligodendrocytes regulates the progression of experimental autoimmune encephalomyelitis.

Multiple sclerosis (MS) is an inflammatory demyelinating disease of the central nervous system (CNS), and experimental autoimmune encephalomyelitis (EAE) is a well-established animal model of the disease. Here, we examined the pathophysiological role of Kallikrein 6 (Klk6), a serine protease produced by oligodendrocytes (OLs), in EAE using Klk6 knockout (Klk6-/-) mice. Compared with Klk6+/+ (wild-type) mice, Klk6-/- mice showed milder EAE symptoms, including delayed onset and milder paralysis. Loss of Klk6 suppressed matrix metalloprotease-9 expression and diminished the infiltration of peripheral inflammatory cells into the CNS by decreasing blood-brain barrier (BBB) permeability and reducing expression levels of inflammatory cytokines, chemokines and their receptors. Scanning electron microscopic analysis revealed demyelination characterized by myelin detachment from the axons in the early phase of EAE progression (days 3-7) in Klk6+/+ mice but not in Klk6-/- mice. Interestingly, anti-MOG (myelin oligodendrocyte glycoprotein) autoantibody was also detected in the cerebrospinal fluid (CSF) and spinal cord on day 3 after MOG immunization. Furthermore, treatment of primary cultured OLs with anti-MOG autoantibody induced oligodendroglial morphological changes and increases in myelin basic protein and Klk6 expression. We also developed a novel enzyme-linked immunoabsorbent assay method for detecting activated KLK6 in human CSF. In human autopsy brain samples, expression of active KLK6 was detected in OLs using an antibody that specifically recognizes the protein's activated form. Taken together, our findings demonstrate that Klk6 secreted by OLs plays a critical role in the pathogenesis of EAE/MS and that it might serve as a potential therapeutic target for MS.

Materials Nanoarchitectonics Using 2D Layered Materials: Recent Developments in the Intercalation Process.

Layered inorganic solids as an attractive classification of 2D materials offer material diversity and a wide range of interesting properties. Layered inorganic solids provide an expandable 2D nanospace between each individual layer, the so called interlayer space, to accommodate/arrange guest species such as molecules, nanoparticles, and polymer chains and design unique nanoarchitectures, resulting in the production of intercalation compounds showing different properties in comparison to those of virgin layered materials and guest species. Layered inorganic solids can also be exfoliated to result in nanosheet production. Further ordering of exfoliated nanosheets is also possible via different methods and normally leads to creating soft materials presenting properties and applications different from that of relatively rigid intercalation compounds. Here, the latest studies and up-to-date developments on the possible techniques of designing novel types of materials using layered inorganic solids are specifically highlighted.

Self-Template-Directed Metal-Organic Frameworks Network and the Derived Honeycomb-Like Carbon Flakes via Confinement Pyrolysis.

Metal-organic frameworks (MOFs) have become a research hotspot since they have been explored as convenient precursors for preparing various multifunctional nanomaterials. However, the preparation of MOF networks with controllable flake morphology in large scale is not realized yet. Herein, a self-template strategy is developed to prepare MOF networks. In this work, layered double-metal hydroxide (LDH) and other layered metal hydroxides are used not only as a scaffold but also as a self-sacrificed metal source. After capturing the abundant metal cations identically from the LDH by the organic linkers, MOF networks are in situ formed. It is interesting that the MOF network-derived carbon materials retain the flake morphology and exhibit a unique honeycomb-like macroporous structure due to the confined shrinkage of the polyhedral facets. The overall properties of the carbon networks are adjustable according to the tailored metal compositions in LDH and the derived MOFs, which are desirable for target-oriented applications as exemplified by the electrochemical application in supercapacitors.