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Improvement of mechanical stability for porous polymer monoliths is one of the prime concerns as represented by the long‐standing research efforts on resorcinol‐formaldehyde (RF) aerogels. To this end, it is imperative not only to tailor mechanically robust porous morphology but also to design macromolecular structure of polymer scaffolds. Previously, we have developed porous RF gels showing a unique mechanical feature combining high mechanical strength and outstanding flexibility against uniaxial compression. Comparison of mechanical properties between the porous gels with varied morphologies has elucidated the influence of porous structure, whereas effects of macromolecular structure still remain elusive. Herein, we have fabricated a series of macroporous phenolic resins from three types of linear prepolymers with phenol pendant groups, poly(4‐vinylphenol) or poly(4‐hydroxystyrene), which differ in molecular‐weight properties, by the sol–gel process in conjunction with spinodal decomposition. The difference in gelation and phase separation behaviors observed for the discrete systems indicates the dissimilar cross‐linked networks developed in the respective gels, which consequently influence the mechanical strength and flexibility against uniaxial compression. This study also demonstrates the improvement of mechanical features by thermal treatment for the porous monoliths derived from the high‐molecular‐weight prepolymer with a view to the application in mechanical energy absorption. [ABSTRACT FROM AUTHOR]

Fatigue can lead to several health issues and is particularly prevalent among elderly individuals with chronic inflammatory conditions. Ninjin'yoeito, a traditional Japanese herbal medicine, is used to address fatigue and malaise, anorexia, and anemia. This study aimed to examine whether relieving inflammation in the brain and skeletal muscle of senescence-accelerated mice prone 8 (SAMP8) could reduce fatigue-like conditions associated with aging. First, SAMP8 mice were divided into two groups, with and without ninjin'yoeito treatment. The ninjin'yoeito-treated group received a diet containing 3% ninjin'yoeito for a period of 4 months starting at 3 months of age. At 7 months of age, all mice underwent motor function, treadmill fatigue, and behavioral tests. They were then euthanized and the skeletal muscle weight, muscle cross-sectional area, and concentration of interleukin (IL)-1β and IL-1 receptor antagonist (IL-1RA) in both the brain and skeletal muscle were measured. The results showed that the ninjin'yoeito-treated group had higher motor function and spontaneous locomotor activity than the untreated group did and ran for significantly longer in the treadmill fatigue test. Moreover, larger muscle cross-sectional area, lower IL-1β concentrations, and higher IL-1RA concentrations were observed in both the brain and skeletal muscle tissues of the ninjin'yoeito-treated group than in the untreated group. The results suggest that ninjin'yoeito improves age-related inflammatory conditions in both the central and peripheral tissues and reduces fatigue. [ABSTRACT FROM AUTHOR]

Synthetic strategies to access high‐valent iridium complexes usually require use of π donating ligands bearing electronegative atoms (e. g. amide or oxide) or σ donating electropositive atoms (e. g. boryl or hydride). Besides the η5‐(methyl)cyclopentadienyl derivatives, high‐valent η1 carbon‐ligated iridium complexes are challenging to synthesize. To meet this challenge, this work reports the oxidation behavior of an all‐carbon‐ligated anionic bis(CCC‐pincer) IrIII complex. Being both σ and π donating, the diaryl dipyrido‐annulated N‐heterocyclic carbene (dpa‐NHC) IrIII complex allowed a stepwise 4e− oxidation sequence. The first 2e− oxidation led to an oxidative coupling of two adjacent aryl groups, resulting in formation of a cationic chiral IrIII complex bearing a CCCC‐tetradentate ligand. A further 2e− oxidation allowed isolation of a high‐valent tricationic complex with a triplet ground state. These results close a synthetic gap for carbon‐ligated iridium complexes and demonstrate the electronic tuning potential of organic π ligands for unusual electronic properties. [ABSTRACT FROM AUTHOR]

Remote ischemic perconditioning (RIPerC) is a novel neuroprotective method against cerebral infarction that has shown efficacy in animal studies but has not been consistently neuroprotective in clinical trials. We focused on the temporal regulation of ischemia–reperfusion by RIPerC to establish an optimal method for RIPerC. Rats were assigned to four groups: 10 min ischemia, 5 min reperfusion; 10 min ischemia, 10 min reperfusion; 5 min ischemia, 10 min reperfusion; and no RIPerC. RIPerC interventions were performed during ischemic stroke, which was induced by a 60-min left middle cerebral artery occlusion. Infarct volume, sensorimotor function, neurological deficits, and cellular expressions of brain-derived neurotrophic factor (BDNF), B-cell lymphoma 2 (Bcl-2), Bcl-2-associated X protein (Bax), and caspase 3 were evaluated 48 h after the induction of ischemia. Terminal deoxynucleotidyl transferase-mediated dUTP-biotin nick-end labeling (TUNEL) was also performed. RIPerC of 10 min ischemia/10 min reperfusion, and 5 min ischemia/10 min reperfusion decreased infarct volume, improved sensorimotor function, decreased Bax, caspase 3, and TUNEL-positive cells, and increased BDNF and Bcl-2 expressions. Our findings suggest RIPerC with a reperfusion time of approximately 10 min exerts its neuroprotective effects via an anti-apoptotic mechanism. This study provides important preliminary data to establish more effective RIPerC interventions. [ABSTRACT FROM AUTHOR]

Thermal insulating materials are of importance for efficient and effective use of heat energy. Porous organic foams are widely employed for this purpose owing to their low thermal conductivity and mass productivity at low cost. However, the poor thermal stability of organic polymers limits their availability within a low temperature range (typically, < 150 °C). In this paper, we demonstrate the one-pot sol–gel synthesis of porous poly(amic acid) (PAA) xerogels and their conversion to porous polyimide (PI) monoliths by thermal imidization. The PAA networks crosslinked with either aromatic or aliphatic triamine and the bicontinuous porous morphology tailored via spinodal decomposition allow the evaporative drying at ambient pressure to obtain low-density PAA xerogels without significant shrinkage. The aromatic crosslinker yields the porous PI monoliths with higher porosity and flexible feature as compared with those prepared with the aliphatic triamine. On the other hand, the porous PI monolith based on the aliphatic crosslinker possesses slightly higher thermal stability owing to the stiffer mechanical property. The durability test results verify the porous PI thermal insulators are available in air at up to ~450 °C for a short period and up to ~350 °C for a long term. Highlights: Porous poly(amic acid) xerogels with bicontinuous morphology are fabricated via the phase separation method. Crosslinked polymer networks are synthesized by using either aromatic or aliphatic triamine crosslinker. Porous polyimide monoliths prepared with the aromatic crosslinker show the lower shrinkage during thermal imidization. The polyimide network crosslinked with the aliphatic triamine exhibits the higher thermal stability against shrinkage. The long-term durability test reveals the availability of the polyimide thermal insulators at up to 350 °C in air. [ABSTRACT FROM AUTHOR]

Purpose: Pain disrupts the daily and social lives of patients with neuropathic pain. Effective treatment of neuropathic pain is difficult. Pharmacological treatments for neuropathic pain are limited, and 40– 60% of patients do not achieve even partial relief of their pain. This study created a chronic constriction injury (CCI) model in rats to examine the effects of regular exercise on neuropathic pain relief, elucidate the mechanism, and determine the effects of neuropathic pain in the hippocampus. Methods: CCI model rats were randomly divided into exercise (Ex) and no exercise (No-Ex) groups. Normal rats (Normal group) were used as controls. The Ex group exercised on a treadmill at 20 m/min for 30 min, 5 days per week for 5 weeks post-CCI. The 50% pain response threshold was assessed by mechanical stimulation. Using immunohistochemistry, we examined activation of glial cells (microglia and astrocytes) by CCR2 and TRAF6 expression in the spinal cord dorsal horn and DCX and PROX1 expression in the hippocampal dentate gyrus. Results: The 50% pain response threshold was significantly lower in the Ex than in the No-Ex group at 5 weeks post-CCI, indicating pain relief. In the spinal cord dorsal horn, IBA1, CCR2, and TRAF6 expression was markedly lower in the Ex group than in the No-Ex group at 3 weeks post-CCI. IBA1, GFAP, CCR2, and TRAF6 expression was markedly lower in the Ex group than in the No-Ex group at 5 weeks post-CCI. In the hippocampus, DCX, but not PROX1, expression was significantly higher in the Ex group than in the No-Ex group at 3 weeks post-CCI. At 5 weeks post-CCI, both DCX and PROX1 expression was markedly increased in the Ex group compared to the No-Ex group. Conclusion: Our findings suggest that regular exercise can improve the neuropathic pain-induced neurogenic dysfunction in the hippocampal dentate gyrus. [ABSTRACT FROM AUTHOR]

A new dimethyl(phenyl)silylborane having a naphthalene-1,8-diaminato (dan) substituent on the boron center, PhMe2Si–B(dan), was synthesized. Owing to the diminished boron Lewis acidity, it is highly stable toward air. Synthetic application of the silylborane to catalytic silylboration and silylation of alkynes is also described. [ABSTRACT FROM AUTHOR]

Porous nonoxide ceramics have exhibited impressive progress in terms of synthesis and applications over the past few decades because of their unique characteristics distinguished from the oxide counterparts. From the synthetic aspect, the preceramic polymer route, where nonoxide ceramics such as carbides and nitrides are produced from molecular precursors, offers exceptional opportunities to elaborate and control the material shape as well as the micro‐ and nanostructures in concert with various techniques. This review presents monolithic ceramic materials based on various reduced phases bearing hierarchical porosity with a focus on those obtained from macroporous preceramic monoliths prepared via the one‐pot sol–gel process accompanied by spinodal decomposition. Here, we highlight two classes of preceramic inorganic–organic hybrid gels: organometallic crosslinked polymers based on poly(silsesquioxane)s and nonorganometallic hybrid networks related to Ti without Ti–C bonds. The polymer‐to‐ceramic conversion processes are discussed with concern for the crystal transition behaviors and the variation of pore properties in different length scales upon heating. In addition, although out of the preceramic polymer category, some examples of inorganic–organic nanocomposite gels with a carbonizable polymer and/or urea for yielding porous metal carbides and nitrides in a monolithic form are introduced as well, which provides extended versatility toward a variety of transition metal systems. [ABSTRACT FROM AUTHOR]

Subarachnoid hemorrhage (SAH) is a catastrophic form of stroke responsible for significant morbidity and mortality. Oxidative stress, inflammation, and neuronal apoptosis are important in the pathogenesis of early brain injury (EBI) following SAH. Preconditioning exercise confers neuroprotective effects, mitigating EBI; however, the basis for such protection is unknown. We investigated the effects of preconditioning exercise on brain damage and sensorimotor function after SAH. Male rats were assigned to either a sham-operated (Sham) group, exercise (Ex) group, or no-exercise (No-Ex) group. After a 3-week exercise program, they underwent SAH by endovascular perforation. Consciousness level, neurological score, and sensorimotor function were studied. The expression of nuclear factor erythroid 2 p45-related factor 2 (Nrf2), heme oxygenase 1 (HO-1), 4-hydroxynonenal (4HNE), nitrotyrosine (NT), ionized calcium-binding adaptor molecule 1 (Iba1), tumor necrosis factor alpha (TNF-α), interleukin 6 (IL-6), interleukin 1β (IL-1β), 14–3-3γ, p-β-catenin Ser37, Bax, and caspase-3 were evaluated by immunohistochemistry or western blotting. The terminal deoxynucleotidyl transferase-mediated biotinylated dUTP nick end labeling (TUNEL) assay was also performed. After SAH, the Ex group had significantly reduced neurological deficits, sensorimotor dysfunction, and consciousness disorder compared with the No-Ex group. Nrf2, HO-1, and 14–3-3γ were significantly higher in the Ex group, while 4HNE, NT, Iba1, TNF-α, IL-6, IL-1β, Bax, caspase-3, and TUNEL-positive cells were significantly lower. Our findings suggest that preconditioning exercise ameliorates EBI after SAH. The expression of 4HNE and NT was reduced by Nrf2/HO-1 pathway activation; additionally, both oxidative stress and inflammation were reduced. Furthermore, preconditioning exercise reduced apoptosis, likely via the 14–3-3γ/p-β-catenin Ser37/Bax/caspase-3 pathway. [ABSTRACT FROM AUTHOR]

Hierarchically porous tin oxide monoliths have been prepared for the first time from a low-cost tin(IV) chloride precursor through an epoxide-mediated sol–gel process in an aprotic solvent N,N-dimethylformamide. Phase separation is induced in the presence of poly(propylene glycol) in the course of polymerization triggered by an acid scavenger, propylene oxide, leading to macroporous tin-based oxyhydroxide monoliths. The resultant macropores are confirmed to be controlled in the size range of 0.9–2.9 μm. Both the post-gelation solvothermal treatment in 2-propanol and calcination in air gave rise to crystallinity and mesoporosity (2.4–103 nm in size with BET surface area up to 261 m2 g−1), and hierarchically porous tin oxide monoliths have been obtained for the first time. The monoliths are demonstrated as a catalyst for the esterification of valeric acid and methanol. [ABSTRACT FROM AUTHOR]

Preconditioning exercise prior to stroke exerts neuroprotection, which is an endogenous strategy that leads the brain cells to express several intrinsic factors and inhibits their apoptosis. However, it is unclear how long these benefits last after exercise cessation. The aim of this study was to investigate the effects of detraining on preconditioning exercise-induced neuroprotective potential after stroke. Rats were trained using a treadmill for aerobic exercise 5 days each week for 3 weeks, and their neuroprotective effects were examined until 3 weeks after exercise cessation. Stroke was induced by 60 min of left middle cerebral artery occlusion at 3 days, 1, 2, and 3 weeks after exercise cessation. Infarct volume, neurological deficits, sensorimotor function, expression levels of brain-derived neurotrophic factor (BDNF), hypoxia-induced factor-1α (HIF-1α), glial fibrillary acidic protein (GFAP), and P2X7 receptors, and apoptosis activity were examined using immunohistochemical and western blot analyses. Preconditioning exercise significantly reduced infarct volume and ameliorated sensorimotor function after stroke, and its beneficial effects were observed until 2 weeks after exercise cessation. The expression level of BDNF in the ischemic brain was significantly upregulated at 3 days after exercise cessation; however, the expression levels of HIF-1α, GFAP, and P2X7 receptor were significantly increased until 2 weeks after exercise cessation; thereby, significant anti-apoptotic effects were lost at 3 weeks of detraining. Our findings suggest that preconditioning exercise-induced neuroprotective potential may be lost shortly after exercise cessation. Neuroprotection through intrinsic protective factors, such as BDNF and HIF-1α, may provide different neuroprotective mechanisms in a time-dependent manner during detraining. [ABSTRACT FROM AUTHOR]

Cobalt manganite‐based hierarchically porous monoliths (HPMs) with three‐dimensionally (3D) interconnected macropores and open nanopores have been prepared via the sol–gel process accompanied by phase separation. The controlled hydrolysis and polycondensation of the brominated metal alkoxides, which are generated from an incomplete reaction between epichlorohydrin and MBr2 (M = Co and Mn) in N,N‐dimethylformamide (DMF), form a monolithic gel based on the two divalent metal cations. The dual‐polymer strategy using polyvinylpyrrolidone (PVP) and poly(ethylene oxide) (PEO) effectively induces the spinodal decomposition, where PVP and PEO are preferentially distributed to the gel phase and fluid phase, respectively, resulting in a porous gel characterized by the co‐continuous structure. The effects of DMF and PVP on the porous morphology derived from the phase separation have been systematically studied. Calcination of the as‐dried gels allows for the crystallization into the spinel phase yielding hierarchically porous CoMn2O4 monoliths, which have been examined in detail by the structural and compositional analyses. [ABSTRACT FROM AUTHOR]

Hierarchically porous monoliths based on copper (Cu), cobalt (Co) and manganese (Mn) oxides with three-dimensionally (3D) interconnected macropores and open nanopores were prepared using metal bromides as precursors via a sol–gel process accompanied by phase separation. The difficulty of gelation for low-valence metal cation was overcome by introducing a highly electronegative Br atom near to the metal atom to control the rates of hydrolysis and polycondensation. The 3D interconnected macropores were obtained using appropriate polymers to induce phase separation. The domain sizes of macropores and skeletons can be controlled by reaction parameters such as concentration and/or average molecular weight of polymers, and the amount of hydrochloric acid. The crystalline metal oxide monoliths with their 3D interconnected macroporous structure preserved were obtained after heat treatment in air. [ABSTRACT FROM AUTHOR]

Hierarchically porous materials with large pores in the micrometer range and small pores in the nanometer range, where the large pores facilitate mass transport and the small pores supply numerous active sites, show superiority to materials with unimodal pores in the fields of separation and adsorption. Among all the methods used to prepare hierarchically porous monoliths (HPMs), the sol–gel process accompanied by spinodal decomposition (or phase separation) shows its advantages such as facile method, no template, precise structural control, good reproducibility, and availability for various kinds of materials. This review focuses on the specific process to prepare various types of HPMs including silica, metal oxides, metal phosphates, and metal–organic hybrids, via the sol–gel process accompanied by spinodal decomposition. The HPMs composed of organic polymer and their carbonized derivatives prepared by polymerization-induced phase separation are also covered in this review as an example of similar morphological formation in purely organic crosslinking reactions. This review directs the most attention to the preparation of monolithic gels (sol–gel process) and the control of macroporous structure (phase separation). Highlights: This review summarizes the preparation of hierarchically porous monoliths with various chemical compositions. The phase separation behaviors and methods of controlling pore structures are described in detail. Latest advances on the formation of porous monolith with low-valence metal oxides as well as metal–organic frameworks compositions are also introduced. [ABSTRACT FROM AUTHOR]

A wide-range control over multimodal pore systems in porous monoliths is a key technology for developing functional materials, as the favorable pore structures in different length scales are required to be tailored depending on their application fields. In the alkoxy-derived sol–gel systems of silica and organosilicates, the synthetic methodology of meso- and macroporous monoliths with tunable pore properties has been developed by combining the supramolecular self-assembly of a Pluronic surfactant and polymerization-induced phase-separation techniques. This strategy has been applied to the sol–gel process of phenolic resins, giving rise to the hierarchically porous polymer gels with ordered mesoporosity and the corresponding carbon monoliths after carbonization. However, the controllable size range has been limited so far. This study has explored the relationship between the starting composition and the bimodal pore properties in further detail aiming at a better control of pore properties in phenolic resins. The enlargement of mesopore size has been achieved, yet associated with broadening the mesopore size distribution and coarsening the macropore morphology, resulting in the particle aggregates. The systematical investigation also reveals that the addition of KCl can improve the micelle arrangement in macroframework and provide the narrower mesopore size distribution. Highlights: Meso- and macroporous RF gels are fabricated by the soft-templating and phase separation method. Mechanism for bimodal pore formation in the progression of polycondensation is proposed. Relationship between the starting composition and meso/macropore geometry has been surveyed. The shape of 2D hexagonal building blocks transforms from cylinder to disk by adding KCl. The addition of KCl effectively improves the size distribution of enlarged mesopores. [ABSTRACT FROM AUTHOR]

We report novel superhydrophobic highly flexible composites based on a doubly cross-linked (DCL) aerogel and carbon nanotubes (CNTs) for strain/pressure sensing. The DCL aerogel/CNT composite is prepared by radical polymerization of vinylmethyldimethoxysilane and vinyldimethylmethoxysilane, respectively, followed by hydrolytic co-polycondensation of the obtained polyvinylmethyldimethoxysilane and polyvinyldimethylmethoxysilane, combined with the incorporation of CNTs. Benefiting from the flexible methyl-rich DCL structure of the aerogel and conductive CNTs, the resultant DCL aerogel/CNT composite combines superhydrophobicity, high compressibility, high bendability, high elasticity, and strain- and pressure-sensitive conductivity. We demonstrate that the composite can be applied as a high-performance strain/pressure sensor for the detection of arterial pulse waves and joint bending with high sensitivity and high durability against humidity. [ABSTRACT FROM AUTHOR]

Background: Midkine (MK) is a multifunctional cytokine found upregulated in the brain in the presence of different disorders characterized by neuroinflammation, including neurodegenerative disorders and ischemia. The neuroinflammatory response to traumatic brain injury (TBI) represents a key secondary injury factor that can result in further neuronal injury. In the present study, we investigated the role of endogenous MK in secondary injury, including neuroinflammation, immune response, and neuronal apoptosis activity, after TBI.Methods: Wild type (Mdk+/+) and MK gene deficient (Mdk-/-) mice were subjected to fluid percussion injury for TBI models and compared at 3, 7, and 14 days after TBI, in terms of the following: brain tissue loss, neurological deficits, microglia response, astrocytosis, expression of proinflammatory M1 and anti-inflammatory M2 microglia/macrophage phenotype markers, and apoptotic activity.Results: As opposed to Mdk+/+ mice, Mdk-/- mice reported a significantly reduced area of brain tissue loss and an improvement in their neurological deficits. The ratios of the Iba1-immunoreactive microglia/macrophages in the perilesional site were significantly decreased in Mdk-/- than in the Mdk+/+ mice at 3 days after TBI. However, the ratios of the glial fibrillary acidic protein immunoreactive area were similar between the two groups. The M1 phenotype marker (CD16/32) immunoreactive areas were significantly reduced in Mdk-/- than in the Mdk+/+ mice. Likewise, the mRNA levels of the M1 phenotype markers (TNF-α, CD11b) were significantly decreased in Mdk-/- mice than in Mdk+/+ mice. Furthermore, flow cytometry analysis identified the M2 markers, i.e., CD163+ macrophages cells and arginase-1+ microglia cells, to be significantly higher in Mdk-/- than in Mdk+/+ mice. Finally, the ratios of apoptotic neurons were significantly decreased in the area surrounding the lesion in Mdk-/- than in Mdk+/+ mice following TBI.Conclusion: Our findings suggest that MK-deficiency reduced tissue infiltration of microglia/macrophages and altered their polarization status thereby reducing neuroinflammation, neuronal apoptosis, and tissue loss and improving neurological outcomes after TBI. Therefore, targeting MK to modulate neuroinflammation may represent a potential therapeutic strategy for TBI management. [ABSTRACT FROM AUTHOR]

Aerogels have many unique properties such as low density and low thermal conductivity, and, in particular, transparent silica aerogels are attractive for thermal insulating windows. Practical applications of silica aerogels, however, have been limited because of their low mechanical strength, and it is still challenging to synthesize transparent and mechanically strong aerogels. Here, we report colorless transparent melamine–formaldehyde (MF) aerogels prepared via a nonaqueous synthetic strategy. The obtained transparent MF aerogel with a density of 0.18 g cm–3 shows significantly higher mechanical strength and a lower thermal conductivity of ca. 13 mW m–1 K–1 compared to conventional silica aerogels with similar density. [ABSTRACT FROM AUTHOR]

We present a two‐step template‐free approach toward monolithic materials with controlled trimodal porous structures with macro‐, meso‐, and micropores. Our method relies on two ordering processes in discrete length scales: 1) Spontaneous formation of macroporous structures in monolithic materials by the sol–gel process through the short‐range ordered self‐assembly of metal–organic frameworks (MOFs), and 2) reorganization of the framework structures in a mediator solution. The Zr‐terephthalate‐based MOF (UiO‐66‐NH2) was adopted as a proof of concept. The self‐assembly‐induced phase separation process offered interconnected macropores with diameters ranging from 0.9 to 1.8 μm. The subsequent reorganization process converted the microporous structure from low crystalline framework to crystalline UiO‐66. The resultant mesopore size within the skeletons was controlled in the range from 9 to 21 nm. This approach provides a novel way of designing spaces from nano‐ to micrometer scale in network‐forming materials. [ABSTRACT FROM AUTHOR]

We present a two‐step template‐free approach toward monolithic materials with controlled trimodal porous structures with macro‐, meso‐, and micropores. Our method relies on two ordering processes in discrete length scales: 1) Spontaneous formation of macroporous structures in monolithic materials by the sol–gel process through the short‐range ordered self‐assembly of metal–organic frameworks (MOFs), and 2) reorganization of the framework structures in a mediator solution. The Zr‐terephthalate‐based MOF (UiO‐66‐NH2) was adopted as a proof of concept. The self‐assembly‐induced phase separation process offered interconnected macropores with diameters ranging from 0.9 to 1.8 μm. The subsequent reorganization process converted the microporous structure from low crystalline framework to crystalline UiO‐66. The resultant mesopore size within the skeletons was controlled in the range from 9 to 21 nm. This approach provides a novel way of designing spaces from nano‐ to micrometer scale in network‐forming materials. [ABSTRACT FROM AUTHOR]

A facile method for the preparation of zinc oxide with three-dimensionally (3D) interconnected macropores has been developed. The Zn-based monolithic gel was obtained using citric acid (CA) as a structure supporter via an epoxide-mediated sol–gel method accompanied by phase separation. The size of the macropores could be controlled by the ratio of methanol to propylene oxide in the starting solution. The Zn-based gel was heat-treated in air with the purpose of removing the organic components and crystallizing the ZnO, finally resulting in pure ZnO (purity ＞90%, with negligible carbon content) with 3D interconnected macropores and an open nanoscale network. The influence of the starting solvent composition on the Zn-based gel morphologies has been examined and discussed based on the chemical compatibility of the Zn–CA complex with other components. [ABSTRACT FROM AUTHOR]

Objective: Preconditioning exercise can exert neuroprotective effects after stroke; however, the effects of exercise intensity, frequency, duration are unknown. We investigated the neuroprotective effect of different frequency preconditioning exercise on neuronal apoptosis after cerebral ischemia in rats. Methods: Rats were divided into the following five groups: 5 times a week of exercise (5/w-Ex) group, 3 times a week of exercise (3/w-Ex) group, once a week of exercise (1/w-Ex) group, no exercise (No-Ex) group, and intact control (control) group. Rats were made to run on a treadmill for 30 min per day at a speed of 25 m/min for 3 weeks. After the running program, the rats were subjected to 60-min left middle cerebral artery occlusion. Two days after ischemia, the cerebral infarct volume, neurological and motor function, Bcl-2-associated X protein (Bax)/B-cell lymphoma 2 (Bcl-2) ratio, expression of caspase-3, and TUNEL positive cells were examined in the cerebral cortex surrounding the ischemic zone. Results: The 3/w-Ex and 5/w-Ex groups showed significantly reduced infarct volumes compared with the No-Ex group, but the 1/w-Ex group did not. In addition, the 3/w-Ex and 5/w-Ex groups had improved neurological scores and sensorimotor function compared with the No-Ex group. The Bax/Bcl-2 ratio, expression of caspase-3, and TUNEL-positive cells significantly decreased in the penumbra area in the 3/w-Ex or 5/w-Ex groups compared with the No-Ex group. Discussion: Our findings suggested that three times or more per week of high-intensity preconditioning exercise exert neuroprotective effects through the downregulation of the Bax/Bcl-2 ratio and caspase-3 activation after stroke. Abbreviations: TUNEL: terminal deoxynucleotidyl transferase-mediated biotinylated dUTP nick and labeling; MCAO:middle cerebral artery occlusion; BAX:Bcl-2-associated X protein; Bcl-2: B-cell lymphoma 2; TTC: 2,3,5-triphenyltetrazorlium chloride [ABSTRACT FROM AUTHOR]

Utilizing the spontaneous wetting of oligomeric silica-phase via phase-separation onto a solid surface in a confined dimension, sub-micrometer thick mesoporous layers have been coated on the surface of nonporous skeletons of preformed macroporous silica gels. The size and volume of mesopores within the layers could be controlled by subsequent aging conditions similarly to those reported for fully porous monolithic silica. Comparison of HPLC efficiencies of these novel type monolithic gels, core-shell silica monoliths, with those of a conventional silica monolith revealed that the retention factor per unit surface area became larger for core-shell silica monoliths. The increase in dynamic accessibility of analyte molecules to the mesopores well explain the improved retention factors in core-shell silica monoliths. Core-shell monoliths with mesoporous layers coated on the surface of micrometer-sized fully-sintered continuous silica skeletons for HPLC separations. Highlights: Macroporous silica monolith with fully sintered skeletons has been used as a host for core-shell silica monolith. Onto the surface of the skeletons, oligomeric silica has been coated utilizing the wetting transition associated with the phase separation in a confined space. Monolithic silica with well-defined continuous macropores and superficially mesoporous silica skeletons was proven to work as an efficient HPLC separation medium. [ABSTRACT FROM AUTHOR]

14-3-3γ is an important early ischemia-inducible protective factor against ischemic cell death in cerebral cortical neurons. We investigated the anti-apoptosis mechanism of enhanced 14-3-3γ mediated by preconditioning exercise-induced brain ischemic tolerance after stroke. Rats were assigned to four groups: exercise and ischemia (Ex group), ischemia and no exercise (No-Ex group), exercise and no ischemia (Ex-only group), and no exercise and ischemia (control group). Rats were trained on a treadmill for 5 days a week for 3 weeks (running speed, 25 m/min; running duration, 30 min/day). After the exercise program, stroke was induced by left middle cerebral artery occlusion. The infarct volume, neurological deficits, and motor function, as well as expression levels of hypoxia-induced factor-1α (HIF-1α), 14-3-3γ, P2X7 receptors, p-β-catenin Ser37, Bax, and caspase 3 were evaluated by immunohistochemistry and western blotting. The expression of HIF-1α and 14-3-3γ significantly increased in neurons and astrocytes in the Ex-only group. HIF-1α was co-expressed with P2X7 receptor- and GFAP-positive astrocytes. After stroke, the Ex group had significantly reduced brain infarction. HIF-1α and 14-3-3γ significantly increased in the Ex group compared to the No-Ex group. In addition, p-β-catenin Ser37 significantly increased following elevated 14-3-3γ; in contrast, Bax and caspase 3 were significantly reduced in the Ex group. Our findings suggest that preconditioning exercise prior to ischemia induces neuron- and astrocyte-mediated brain ischemic tolerance through increased expression of HIF-1α and 14-3-3γ, which are intrinsic protective factors; the upregulated 14-3-3γ induced by preconditioning exercise reduces ischemic neuronal cell death through the 14-3-3γ/p-β-catenin Ser37/Bax/caspase 3 anti-apoptotic pathway. [ABSTRACT FROM AUTHOR]

Abstract: Here, we overview the developments in the past decade made on organic-inorganic hybrid aerogels and xerogels based on silicone (polyorganosiloxanes) through persistent works by the authors to increase the mechanical strength and flexibility and add functionality. Polymethylsilsesquioxane (PMSQ, CH3SiO3/2) has been found to show unusual strength and flexibility against compression, and their bending properties can also be improved by several strategies. Silicone-based networks with organic bridges between inorganic moieties are also beneficial for these improvements. In particular, organic bridges with a higher fraction and more extended length have been found to allow higher durability against large deformations. In addition, functional groups such as vinyl, chloromethyl, and amino can readily be introduced by starting from organoalkoxysilanes with these functional substituents (e.g., FG−Si(OR)3 or (RO)3Si−FG−Si(OR)3, where FG shows an organic substituent containing functional groups and R is typically methyl or ethyl), and other functional groups such as carboxyl can be introduced by post-gelation modifications on the pre-installed FG in the network. Possibilities in applications such as thermal insulators, photoluminescent media, and photocatalysts are also discussed. Silicone-based organic-inorganic hybrid aerogels developed by the authors are overviewed.Improved mechanical flexibility allows ambient pressure drying to yield aerogel-like xerogels.Reactive organic functional groups can be introduced in the hybrid networks. [ABSTRACT FROM AUTHOR]

Hierarchically porous magnesium oxide, MgO, monoliths with a well-defined continuous macroporous structure have been synthesized via the sol-gel route accompanied by phase separation. Magnesium chloride hexahydrate was used as a precursor, and propylene oxide was used as an acid scavenger to raise the pH of a reaction solution homogenously. In order to obtain a crack-free monolith after heating in air, poly(vinylpyrrolidone), PVP, was employed as a scaffold of the skeleton as well as a phase separation controller to form the continuous macropores with higher homogeneity. Due to the moderate hydrogen-bonding interaction with magnesium hydroxide, PVP reinforces the gel network essentially composed of fine grained magnesium hydroxide. Even after the removal of all organic components by calcination, the porous gel samples maintained their monolithic form. On the other hand, an additional incorporation of 1,3,5-benzenetricarboxylic acid, H3BTC, was found to be effective in suppressing the oriented growth of the micrometer-sized crystalline phase. The polycrystalline MgO monoliths with specific surface area of 185, 64, and 48 m2 g−1 were prepared after heating at 400, 500, and 600 °C in air, respectively.Appearances (upper) and SEM images(lower) of monolithic MgO-based gel before and after heat-treatment. [ABSTRACT FROM AUTHOR]

Abstract: Hierarchically porous spinel-type binary metal oxide MgAl2O4 with cocontinuous skeletons and interconnected macropores has been synthesized by a facile sol-gel method accompanied by phase separation, in which poly (ethylene oxide) (PEO) works as phase separation inducer to form micrometer-scale phase-separated macrochannels at the same time of sol-gel transition. The obtained xerogels exhibit in the form of a monolith with well-defined macropores and cocontinuous dense skeletons by adjusting the amount of PEO. The xerogel and those heat-treated at or below 600 °C are amorphous, and heat-treatment at or above 700 °C allows the precipitation of complete crystalline MgAl2O4 spinel with a macropore size of 0.7-0.9 μm, a porosity of 60-70%, and a BET surface area of 40-80 m2 g−1, without spoiling the macrostructure of monoliths. Three anionic dyes and two cationic dyes are selected as targeted adsorbates to investigate the selective adsorption ability of a hierarchically porous MgAl2O4 spinel. The resultant MgAl2O4 spinel shows a high affinity and adsorption rate toward anionic dyes Congo Red, Methyl Orange, and Methyl Blue. The maximum adsorption capacity of MgAl2O4 spinel toward these three anionic dyes are 2721.6 mg g−1 for Congo Red, 2469.7 mg g−1 for Methyl Orange, and 6771.9 mg g−1 for Methyl Blue, respectively.The strong electrostatic interaction as well as hydrogen bond between the positively charged sites in hierarchically porous MgAl2O4 spinel and amino groups or negatively charged sulfonate groups (-SO3-) in the anionic dyes. The macropores provide delivery channels and the mesopores produce enough adsorption sites. Hierarchically porous spinel-type binary metal oxide MgAl2O4 has facilely been synthesized by a sol-gel method accompanied by phase separation.The resultant MgAl2O4 spinel has high adsorption capacity toward anionic dyes Congo Red, Methyl Orange, and Methyl Blue.A probable adsorption mechanism based on the strong electrostatic attraction and hydrogen bonding is discussed. [ABSTRACT FROM AUTHOR]

Abstract: Aerogels are porous materials but show poor mechanical properties and limited functionality, which significantly restrict their practical applications. Preparation of highly bendable and processable aerogels with multifunctionality remains a challenge. Herein we report unprecedented superflexible aerogels based on polyvinylpolydimethylsiloxane (PVPDMS) networks, PVPDMS/polyvinylpolymethylsiloxane (PVPMS) copolymer networks, and PVPDMS/PVPMS/graphene nanocomposites by a facile radical polymerization/hydrolytic polycondensation strategy and ambient pressure drying or freeze drying. The aerogels have a doubly cross‐linked organic–inorganic network structure consisting of flexible polydimethylsiloxanes and hydrocarbon chains with tunable cross‐linking density, tunable pore size and bulk density. They have a high hydrophobicity and superflexibility and combine selective absorption, efficient separation of oil and water, thermal superinsulation, and strain sensing. [ABSTRACT FROM AUTHOR]

Abstract: Aerogels are porous materials but show poor mechanical properties and limited functionality, which significantly restrict their practical applications. Preparation of highly bendable and processable aerogels with multifunctionality remains a challenge. Herein we report unprecedented superflexible aerogels based on polyvinylpolydimethylsiloxane (PVPDMS) networks, PVPDMS/polyvinylpolymethylsiloxane (PVPMS) copolymer networks, and PVPDMS/PVPMS/graphene nanocomposites by a facile radical polymerization/hydrolytic polycondensation strategy and ambient pressure drying or freeze drying. The aerogels have a doubly cross‐linked organic–inorganic network structure consisting of flexible polydimethylsiloxanes and hydrocarbon chains with tunable cross‐linking density, tunable pore size and bulk density. They have a high hydrophobicity and superflexibility and combine selective absorption, efficient separation of oil and water, thermal superinsulation, and strain sensing. [ABSTRACT FROM AUTHOR]

Iron(iii) oxyhydroxide and oxide monoliths with controlled multiscale porosity have been successfully fabricated via the sol–gel process accompanied by phase separation. The size of macropores was controlled by synthesis parameters such as starting compositions. The as-dried iron(iii) oxyhydroxide monoliths were amorphous and possessed surface areas over 340 m2 g−1, of which mesostructures could be further controlled by a heat-treatment at 250–350 °C without collapse of macrostructures and monolithic forms. When the as-dried gel was heated at 300 °C, the resultant gel transformed to crystalline α-Fe2O3 and exhibited a specific surface area of 124 m2 g−1. Heat-treatment at 350 °C resulted in the broadened size distribution of mesopores. The adsorption behavior of Congo red has revealed that the interconnected macroporous structure contributed to faster diffusion and better accessibility in a continuous flow-through set up, and the crack-free monolithic forms accounted for an advantageous use of the flow-through adsorbents. [ABSTRACT FROM AUTHOR]

Background: Exercise regimens are established methods that can relieve neuropathic pain. However, the relationship between frequency and intensity of exercise and multiple cellular responses of exercise-induced alleviation of neuropathic pain is still unclear. We examined the influence of exercise frequency on neuropathic pain and the intracellular responses in a sciatic nerve chronic constriction injury (CCI) model. Materials and methods: Rats were assigned to four groups as follows: CCI and high-frequency exercise (HFE group), CCI and low-frequency exercise (LFE group), CCI and no exercise (No-Ex group), and naive animals (control group). Rats ran on a treadmill, at a speed of 20 m/min, for 30 min, for 5 (HFE) or 3 (LFE) days a week, for a total of 5 weeks. The 50% withdrawal threshold was evaluated for mechanical sensitivity. The activation of glial cells (microglia and astrocytes), expression of brain-derived neurotrophic factor (BDNF) and µ-opioid receptor in the spinal dorsal horn and endogenous opioid in the midbrain were examined using immunohistochemistry. Opioid receptor antagonists (naloxone) were administered using intraperitoneal injection. Results: The development of neuropathic pain was related to the activation of glial cells, increased BDNF expression, and downregulation of the µ-opioid receptor in the ipsilateral spinal dorsal horn. In the No-Ex group, neuropathic pain showed the highest level of mechanical hypersensitivity at 2 weeks, which improved slightly until 5 weeks after CCI. In both exercise groups, the alleviation of neuropathic pain was accelerated through the regulation of glial activation, BDNF expression, and the endogenous opioid system. The expression of BDNF and endogenous opioid in relation to exercise-induced alleviation of neuropathic pain differed in the HFE and LFE groups. The effects of exercise-induced alleviation of mechanical hypersensitivity were reversed by the administration of naloxone. Conclusion: The LFE and HFE program reduced neuropathic pain. Our findings indicated that aerobic exercise-induced alleviated neuropathic pain through the regulation of glial cell activation, expression of BDNF in the ipsilateral spinal dorsal horn, and the endogenous opioid system. [ABSTRACT FROM AUTHOR]

The I Journal of Sol-Gel Science and Technology i , JSST, was established in 1993 with Professor Sakka as sole editor, by Kluwer Academic Publishers. In 1988, the first book on the sol-gel method in Japanese, " I Science of Sol-Gel Method: Low-temperature synthesis of functional glass and ceramics i ", was written by Professor Sakka, and in 1990, " I Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing i " was co-authored by Drs C.J. Brinker and G.W. Scherer. Companies involved in the production of glass/ceramic materials started to launch sol-gel research activities after the workshop. [Extracted from the article]

Phase separation control is an important factor to prepare a porous monolith by an aqueous sol-gel reaction. Here, we report a surfactant-free synthesis method to obtain hydrophobic polymethylsilsesquioxane aerogels by copolymerizing a cationic-functionalized alkoxysilane N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride. The resultant materials have low-density, high visible-light transmittance, and high thermal insulating equivalent to those of prepared under the presence of surfactant. [ABSTRACT FROM AUTHOR]

Aerogels are attracting increasing attention due to their high thermal insulation ability as well as unique properties such as high porosity, surface area, and transparency. However, low mechanical strengths, originating from their unique porous structure, impede handling, formability, mass production, and extended applications. This minireview focuses on the strengthening of aerogels by several organic-inorganic hybridization strategies. In particular, successful strengthening methodologies, which employ organo-substituted alkoxysilanes as the single precursor for the sol-gel preparations, developed by the authors are highlighted. Moreover, improvements in compressive strength and elasticity lead to monolithic aerogel-like xerogels through ambient pressure drying. Correlations between structures in different length scales (e.g., molecular, network, and pore structure levels) and resultant mechanical properties are discussed for further understandings and better design toward mechanically improved aerogels/xerogels and their applications. [ABSTRACT FROM AUTHOR]

Systematic investigations on the effect of synthetic conditions onto the properties of polyvinylsilsesquioxane (CH=CHSiO) aerogels have been conducted. As previously reported, transparent polyvinylsilsesquioxane aerogels can be obtained by utilizing a liquid surfactant as a solvent and a two-step sol-gel reaction involving hydrolysis catalyzed by a strong acid and subsequent polycondensation by a strong base. In this study, effects of base catalyst, gelation and aging conditions, amount of surfactant and concentration of acid catalyst have been investigated. With the optimized synthetic condition, the value of light transmittance reaches as high as 70% (at the wavelength of 550 nm for a 10-mm thick sample). Applicability of addition reactions utilizing thiol-ene reactions and hydrosilylation has also been surveyed. Thiol-ene reactions are relatively effective and can modify surface hydrophobicity and mechanical properties of polyvinylsilsesquioxane aerogels. In the case of hydrosilylation, a partial addition of a hydrosilane compound onto the polyvinylsilsesquioxane gel surface can be observed. Addition reactions, in particular thiol-ene reactions, are found to be profitable for implementing chemical functionality on the transparent aerogels. Graphical Abstract: [ABSTRACT FROM AUTHOR]

Low-density, transparent aerogels based on a hexylene-bridged polysilsesquioxane ([OSi-(CH)-SiO]) network have been prepared for the first time via a simple sol-gel process. An optimized base-catalyzed one-step hydrolysis-polycondensation process of a bridged alkoxysilane precursor 1,6-bis(trimethoxysilyl)hexane in a low-polarity solvent N, N-dimethylformamide allows for the formation of a pore structure of a length scale of several tens nanometers, resulting in low-density, transparent aerogels after supercritical drying. Because of the incorporated organic moiety that bridges the silicon atoms in the network, these aerogels show higher flexibility and strength against compression and bending as compared to silica aerogel counterparts. In addition, minimizing the residual silanol groups in the network by a surface modification with hexamethyldisilazane has further improved resilience after compression and bending flexibility and strength, due to the decreased chance of the irreversible formation of the siloxane bonds upon compression. The resulting trimethylsilylated hydrophobic gels have been subjected to ambient pressure drying to obtain xerogels, resulting in low-density (0.13 g cm, 90 % porosity), transparent (71 % transmittance) xerogels. These results are promising for the development of transparent thermal superinsulators applicable to window insulating systems that manage heat transfer in a more efficient way. Graphical Abstract: [ABSTRACT FROM AUTHOR]

Yttria-stabilized zirconia monoliths with well-defined macropores and high porosity have been successfully fabricated via sol-gel process accompanied by phase separation. Propylene oxide acts as an acid consumer to mediate sol-gel process, and poly (ethylene oxide) is used to induce phase separation. Ethylene glycol is applied as chelating agent, and formamide serves as drying control chemical additive to inhibit cracking during drying stage. Proper proportion of the starting compositions allows the generation of well-defined macroporous YSZ monoliths with co-continuous skeletons and porosity as high as more than 60 %. The dried gels are amorphous and crystalline of ZrO precipitates after heat treatment between 400 and 1200 °C without formation of monoclinic ZrO, which indicating a wide application prospects. [ABSTRACT FROM AUTHOR]

Hierarchically porous titanium phosphate monoliths combining well-defined co-continuous macropores and accessible large mesopores have been synthesized for the first time via a sol–gel process accompanied by phase separation using titanium oxysulfate and phosphoric acid as precursors. The macropore size was tunable over a broad range from 0.6 μm to 10 μm by changing the starting composition, while the mesopore size and the specific surface area of the as-synthesized amorphous monoliths are 21 nm and 320 m2 g−1, respectively. Crystallization of the gel network can be induced in two different ways. Calcination at elevated temperature (800 °C) leads to the formation of TiP2O7 and the collapse of both the macro- and meso-structures, while the solvothermal treatment of the as-synthesized gel in ethylene glycol leads to the formation of platy crystals of titanium phosphate with a layered structure at relatively low temperature. The titanium phosphate monoliths with a hierarchically porous structure are expected to be useful in various applications such as continuous-flow catalysis, water remediation and ion batteries. [ABSTRACT FROM AUTHOR]

Spherical capsules have been used in various fields because of their many advantages. In many industrial applications, hydrophobic hard resins (e.g., polyacrylate, epoxy and polystyrene) are used as a shell material for stable packaging of ingredients within capsules. However, it is difficult to encapsulate ingredients in such capsules without loss by conventional techniques. The purpose of this study was to encapsulate hydrophobic ingredients within polyacrylate resin capsules with ultrahigh efficiency. In our methodology, a small volume of resin monomer solution containing the ingredients was first placed on a superoleophobic material and the resulting spherical droplets were then solidified by polymerization of the monomer. Doxorubicin (an anticancer drug), α-tocopherol (an antioxidant) and tetradecane (a phase change material used for heat storage) could be encapsulated in spherical hard capsules with almost no loss by heat and photopolymerization. We showed that tetradecane in the capsules had almost identical thermal properties to pure tetradecane. These results demonstrate that our technique is promising for encapsulation of hydrophobic ingredients in hard resin capsules. [ABSTRACT FROM AUTHOR]

Hard carbons have immense potential as anode materials for Na-ion batteries, because the expanded graphene interlayers and nanovoids between randomly stacked aromatic fragments can accommodate a substantial amount of sodium. However, the large irreversible capacity in the first cycle still remains as a significant issue in terms of a practicable battery technology. Here, we show that hard carbon electrodes derived from a common phenol resin deliver a high reversible capacity within the narrow potential range of 0.1-0.005 V (vs. Na+/Na) and an excellent initial coulombic efficiency up to 95 %. The former allows the sustainable high voltage, whereas the latter minimizes the amount of unavailable Na+ in a closed cell. The findings in this work put forward a guideline for manufacturing hard carbon electrodes, which goes against the current trend of nanostructuring and downsizing. [ABSTRACT FROM AUTHOR]