Surfactant-Free, Size-Controllable, and Scalable Green Synthesis of ZIF-8 Particles with Narrow Size Distribution by Tuning Key Reaction Parameters in Water Solvent.

The chemical/physical properties and reliable performance of nanoporous materials are strongly influenced by the particle size and corresponding distribution. Among many types of MOFs, ZIF-8, is still widely used and many studies have been conducted to control the particle size and uniformity of ZIF-8 using surfactants and organic solvents. However, the use of surfactants and organic solvents process is expensive and may cause environmental pollution. For the first time, in this paper, a surfactant-free, size-controllable, and scalable green synthesis method of ZIF-8 particles is reported using four reaction parameters (temperature, concentration, pouring time, and reactant ratio) that affect the formation of nuclei and growth of ZIF-8 crystals. The as-synthesized ZIF-8 nanoparticles show great uniformity and controllable particle sizes in the wide range of 147-915 nm. In addition, a 2 L large-scale synthesis of ZIF-8 with narrow size distribution is developed by finely tuned particle size in water without any additives. To demonstrate the efficient utilization of nanopores according to the particle size and size distribution, an adsorption test is conducted on the ZIF-8 nanoparticles. This study will support the synthesis of size-controlled ZIF-8 with narrow size distribution and their composites for achieving high performance in the emerging applications.

Sunlight-driven and gram-scale vanillin production via Mn-defected γ-MnO2 catalyst in aqueous environment.

The production of vanillin from biomass offers a sustainable route for synthesizing daily-use chemicals. However, achieving sunlight-driven vanillin synthesis through H2O activation in an aqueous environment poses challenges due to the high barrier of H2O dissociation. In this study, we have successfully developed an efficient approach for gram-scale vanillin synthesis in an aqueous reaction, employing Mn-defected γ-MnO2 as a photocatalyst at room temperature. Density functional theory calculations reveal that the presence of defective Mn species (Mn3+) significantly enhances the adsorption of vanillyl alcohol and H2O onto the surface of the γ-MnO2 catalyst. Hydroxyl radical (˙OH) species are formed through H2O activation with the assistance of sunlight, playing a pivotal role as oxygen-reactive species in the oxidation of vanillyl alcohol into vanillin. The Mn-defected γ-MnO2 catalyst exhibits exceptional performance, achieving up to 93.4% conversion of vanillyl alcohol and 95.7% selectivity of vanillin under sunlight. Notably, even in a laboratory setting during the daytime, the Mn-defected γ-MnO2 catalyst demonstrates significantly higher catalytic performance compared to the dark environment. This work presents a highly effective and promising strategy for low-cost and environmentally benign vanillin synthesis.

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.

Materials Space-Tectonics: Atomic-level Compositional and Spatial Control Methodologies for Synthesis of Future Materials.

Reactions occurring at surfaces and interfaces necessitate the creation of well-designed surface and interfacial structures. To achieve a combination of bulk material (i.e., framework) and void spaces, a meticulous process of "nano-architecting" of the available space is necessary. Conventional porous materials such as mesoporous silica, zeolites, and metal-organic frameworks lack advanced cooperative functionalities owing to their largely monotonous pore geometries and limited conductivities. To overcome these limitations and develop functional structures with surface-specific functions, the novel materials space-tectonics methodology has been proposed for future materials synthesis. This review summarizes recent examples of materials synthesis based on designing building blocks (i.e., tectons) and their hybridization, along with practical guidelines for implementing materials syntheses and state-of-the-art examples of practical applications. Lastly, the potential integration of materials space-tectonics with emerging technologies, such as materials informatics, is discussed.

Mesoporous Semiconductive Bi2Se3 Films.

Bi2Se3 is a semiconductive material possessing a bandgap of 0.3 eV, and its unique band structure has paved the way for diverse applications. Herein, we demonstrate a robust platform for synthesizing mesoporous Bi2Se3 films with uniform pore sizes via electrodeposition. Block copolymer micelles act as soft templates in the electrolyte to create a 3D porous nanoarchitecture. By controlling the length of the block copolymer, the pore size is adjusted to 9 and 17 nm precisely. The nonporous Bi2Se3 film exhibits a tunneling current in a vertical direction of 52.0 nA, but upon introducing porosity (9 nm pores), the tunneling current increases significantly to 684.6 nA, suggesting that the conductivity of Bi2Se3 films is dependent on the pore structure and surface area. The abundant porous architecture exposes a larger surface area of Bi2Se3 to the surrounding air within the same volume, thereby augmenting its metallic properties.

Metal-organic frameworks and their derivatives for metal-ion (Li, Na, K and Zn) hybrid capacitors.

Metal-ion hybrid capacitors (MIHCs) hold particular promise for next-generation energy storage technologies, which bridge the gap between the high energy density of conventional batteries and the high power density and long lifespan of supercapacitors (SCs). However, the achieved electrochemical performance of available MIHCs is still far from practical requirements. This is primarily attributed to the mismatch in capacity and reaction kinetics between the cathode and anode. In this regard, metal-organic frameworks (MOFs) and their derivatives offer great opportunities for high-performance MIHCs due to their high specific surface area, high porosity, topological diversity, and designable functional sites. In this review, instead of simply enumerating, we critically summarize the recent progress of MOFs and their derivatives in MIHCs (Li, Na, K, and Zn), while emphasizing the relationship between the structure/composition and electrochemical performance. In addition, existing issues and some representative design strategies are highlighted to inspire breaking through existing limitations. Finally, a brief conclusion and outlook are presented, along with current challenges and future opportunities for MOFs and their derivatives in MIHCs.

Recent progress of functional metal-organic framework materials for water treatment using sulfate radicals.

Human health is being threatened by the ever-increasing water pollution. Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) are rapidly being developed and gaining considerable attention due to their high oxidation potential and selectivity as a way to purify water by degrading organic contaminants in it. Among the catalytic materials that can activate the precursor to generate SO4•-, metal-organic frameworks (MOFs) are the most promising heterogeneous catalytic material in SR-AOPs because of their various structure possibilities, large surface area, ordered porous structure, and regular activation sites. Herein, an in-depth overview of MOFs and their derivatives for water purification with SR-AOPs is provided. The latest studies on pristine MOFs, MOF composites, and MOF derivatives (metal oxides, metal-carbon hybrids, and carbon materials) are summarized. The mechanisms of decomposition of pollutants in water via radical and non-radical pathways are also discussed. This review suggests future research directions for water purification through MOF-based SR-AOP.

Facile preparation of nanocellulose/Zn-MOF-based catalytic filter for water purification by oxidation process.

Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) have recently attracted much attention due to their potential in degrading organic pollutants. Metal-organic frameworks (MOFs) have been reported as effective materials to generate SO4•-. However, it is challenging to separate and recover the dispersed MOF particles from the reaction solution when MOFs are used alone. We used cellulose nanofibers (CNFs) as a porous filter template to immobilize Zn-based MOF, zeolitic imidazolate framework-8 (ZIF-8), and obtained a catalytic composite membrane having peroxymonosulfate (PMS) activating function to produce SO4•-. The CNF was effective in holding ZIF-8 nanoparticle and making a durable porous filter. The activated PMS-produced •OH and SO4•- radicals from ZIF-8 play an important role in the catalytic reaction. More than 90% of methylene blue and rhodamine B was degraded by ZIF-8/CNFs composite membrane in the PMS environment within 60 min. The ZIF-8/CNFs catalytic filters can be used several times without performance reduction for organic dye degradation. The results show that ZIF-8/CNFs catalytic membrane can be separated from organic pollution system quickly and used for the efficient separation and recovery of MOF particle-based catalytic materials. Therefore, this study provides a new perspective for fabricating the MOFs particles-immobilized catalytic filter by biomass nanocellulose-based materials for water purification. This method can be used for facile fabrication of the cellulose-based porous functional filter and open diverse applications.

Antifibrosis treatment by inhibition of VEGF, FGF, and PDGF receptors improves bladder wall remodeling and detrusor overactivity in association with modulation of C-fiber afferent activity in mice with spinal cord injury.

AIMS: Spinal cord injury (SCI) above the sacral level causes bladder dysfunction and remodeling with fibrosis. This study examined the antifibrotic effects using nintedanib, an inhibitor of vascular endothelial growth factor, fibroblast growth factor, and platelet-derived growth factor receptors, on detrusor overactivity (DO) and bladder fibrosis, as well as the modulation mechanisms of C-fiber afferent pathways. METHODS: Thirty female C57BL/6 mice were divided into group A (spinal intact), group B (SCI with vehicle), and group C (SCI with nintedanib). At 2 weeks after SCI, vehicle or 50 mg/kg nintedanib was administered subcutaneously for 2 weeks. Then, cystometry was conducted, followed by RT-PCR measurements of fibrosis-related molecules, muscarinic, ß-adrenergic, TRP and purinergic receptors in the bladder or L6-S1 dorsal root ganglia (DRG). Trichrome stain and Western blot analysis of transforming growth factor-beta and fibronectin were performed in the bladder. TRPV1 expression in L6 DRG was measured by immunohistochemistry. RESULTS: In cystometry, intercontraction intervals, nonvoiding contractions, voided volume, and voiding efficiency were significantly improved in group C versus group B. RT-PCR, Western blotting, and trichrome staining revealed the fibrotic changes in the bladder of group B, which was improved in group C. Increased messenger RNA levels of TRPV1, TRPA1, P2X2 , and P2X3 in DRG of group B were significantly decreased in group C. TRPV1 immunoreactivity in DRG was increased in group B, but decreased in group C. CONCLUSIONS: Nintedanib improves storage and voiding dysfunctions and bladder fibrosis in SCI mice. Also, nintedanib-induced improvement of DO is associated with reduced expression of C-fiber afferent markers, suggesting the modulation of bladder C-fiber afferent activity.

Hypoxia-inducible factor 2α is a novel inhibitor of chondrocyte maturation.

Hypoxic environment is essential for chondrocyte maturation and longitudinal bone growth. Although hypoxia-inducible factor 1 alpha (Hif-1α) has been known as a key player for chondrocyte survival and function, the function of Hif-2α in cartilage is mechanistically and clinically relevant but remains unknown. Here we demonstrated that Hif-2α was a novel inhibitor of chondrocyte maturation through downregulation of Runx2 stability. Mechanistically, Hif-2α binding to Runx2 inhibited chondrocyte maturation by Runx2 degradation through disrupting Runx2/Cbfß complex formation. The Hif-2α-mediated-Runx2 degradation could be rescued by Cbfß transfection due to the increase of Runx2/Cbfß complex formation. Consistently, mesenchymal cells derived from Hif-2α heterozygous mice were more rapidly differentiated into hypertrophic chondrocytes than those of wild-type mice in a micromass culture system. Collectively, these findings demonstrate that Hif-2α is a novel inhibitor for chondrocyte maturation by disrupting Runx2/Cbfß complex formation and consequential regulatory activity.

Comparison of volume-controlled, pressure-controlled, and pressure-controlled volume-guaranteed ventilation during robot-assisted laparoscopic gynecologic surgery in the Trendelenburg position.

Background: Pressure-controlled ventilation volume-guaranteed (PCV-VG) is being increasingly used for ventilation during general anesthesia. Carbon dioxide (CO2) pneumoperitoneum in the Trendelenburg position is routinely used during robot-assisted laparoscopic gynecologic surgery. Here, we hypothesized that PCV-VG would reduce peak inspiratory pressure (Ppeak), compared to volume-controlled ventilation (VCV) and pressure-controlled ventilation (PCV). Methods: In total, 60 patients were enrolled in this study and randomly assigned to receive VCV, PCV, or PCV-VG. Hemodynamic variables, respiratory variables, and arterial blood gases were measured in the supine position 15 minutes after the induction of anesthesia (T0), 30 and 60 minutes after CO2 pneumoperitoneum and Trendelenburg positioning (T1 and T2, respectively), and 15 minutes after placement in the supine position at the end of anesthesia (T3). Results: The Ppeak was higher in the VCV group than in the PCV and PCV-VG groups (p=0.011). Mean inspiratory pressure (Pmean) was higher in the PCV and PCV-VG groups than in the VCV group (p<0.001). Dynamic lung compliance (Cdyn) was lower in the VCV group than in the PCV and PCV-VG groups (p=0.001). Conclusion: Compared to VCV, PCV and PCV-VG provided lower Ppeak, higher Pmean, and improved Cdyn, without significant differences in hemodynamic variables or arterial blood gas results during robot-assisted laparoscopic gynecologic surgery with Trendelenburg position.

Transglutaminase-2 regulates Wnt and FoxO3a signaling to determine the severity of osteoarthritis.

Transglutaminase 2 (TG2), also known as tissue transglutaminase, is a calcium-dependent enzyme that has a variety of intracellular and extracellular substrates. TG2 not only increases in osteoarthritis (OA) tissue but also affects the progression of OA. However, it is still unclear how TG2 affects cartilage degradation in OA at the molecular level. Surgically induced OA lead to an increase of TG2 in the articular cartilage and growth plate, and it was dependent on TGFß1 in primary chondrocytes. The inhibition of TG2 enzymatic activity with intra-articular injection of ZDON, the peptide-based specific TG2 inhibitor, ameliorated the severity of surgically induced OA as well as the expression of MMP-3 and MMP-13. ZDON attenuated MMP-3 and MMP-13 expression in TGFß- and calcium ionophore-treated chondrocytes in a Runx2-independent manner. TG2 inhibition with ZDON suppressed canonical Wnt signaling through a reduction of ß-catenin, which was mediated by ubiquitination-dependent proteasomal degradation. In addition, TG2 activation by a calcium ionophore enhanced the phosphorylation of AMPK and FoxO3a and the nuclear translocation of FoxO3a, which was responsible for the increase in MMP-13. In conclusion, TG2 plays an important role in the pathogenesis of OA as a major catabolic mediator that affects the stability of ß-catenin and FoxO3a-mediated MMP-13 production.

Transparent Photothermal Heaters from a Soluble NIR-Absorbing Diimmonium Salt.

While numerous near-infrared (NIR) materials have emerged, most of them are strongly colored or black due to the absorption band or tails in the visible region. Here, a highly transparent and soluble NIR-absorbing ionic salt, isobutyl-substituted diimmonium borate (IDI), is synthesized and fabricated, through a solution process, as a thin film that shows a transmittance of over 93% in the whole visible region. A transparent photothermal (PT) film heater is fabricated with the IDI-doped polymer solution, which shows a photothermal conversion efficiency (ηPT ) of 75.2%. Additionally, the prepared PT heater shows a high water evaporation conversion efficiency (ηw ) of 68.8% upon exposure to a 1064 nm laser. Furthermore, the transparent IDI film affords the development of a wireless transparent actuator for the first time, generating a bending angle over 75°, with over 2700 bending cycles. The transparent IDI film creates a hot transparent Venus flytrap and a colorful or fluorescent actuator upon the addition of colorants without losing the actuation properties.

Degrading products of chondroitin sulfate can induce hypertrophy-like changes and MMP-13/ADAMTS5 production in chondrocytes.

Chondroitin sulfate (CS) is the most abundant glycosaminoglycan (GAG) in articular cartilage and the loss of CS-GAG occurs early in OA. As a major component of perichondral matrix interacting directly with chondrocytes, the active turnover of CS can affect to break the homeostasis of chondrocytes. Here we employ CS-based 3-dimensional (3D) hydrogel scaffold system to investigate how the degradation products of CS affect the catabolic phenotype of chondrocytes. The breakdown of CS-based ECM by the chondroitinase ABC (ChABC) resulted in a hypertrophy-like morphologic change in chondrocytes, which was accompanied by catabolic phenotypes, including increased MMP-13 and ADAMTS5 expression, nitric oxide (NO) production and oxidative stress. The inhibition of Toll-like receptor 2 (TLR2) or TLR4 with OxPAPC (TLR2 and TLR4 dual inhibitor) and LPS-RS (TLR4-MD2 inhibitor) ameliorated these catabolic phenotypes of chondrocytes by CS-ECM degradation, suggesting a role of CS breakdown products as damage-associated molecular patterns (DAMPs). As downstream signals of TLRs, MAP kinases, NF-kB, NO and STAT3-related signals were responsible for the catabolic phenotypes of chondrocytes associated with ECM degradation. NO in turn reinforced the activation of MAP kinases as well as NFkB signaling pathway. Thus, these results propose that the breakdown product of CS-GAG can recapitulate the catabolic phenotypes of OA.

Enhanced Activation of Rac1/Cdc42 and MITF Leads to Augmented Osteoclastogenesis in Autosomal Dominant Osteopetrosis Type II.

The autosomal dominant osteopetrosis type II (ADOII) caused by the mutation of chloride channel 7 (ClC-7) gene is the most common form of adult-onset osteopetrosis. Despite dysfunctional bone resorption, an augmented osteoclast differentiation was reported recently in ADOII patients. DNA sequencing analysis of the ADOII patient's ClC-7 gene identified a known heterozygous mutation, c.643G>A in exon 7, encoding p.Gly215Arg. In vitro osteoclast differentiation from the ADOII patient's peripheral blood mononuclear cells (PBMCs) increased compared with control despite their dysfunctional bone resorbing capacity. Osteoclasts from the ADOII patient's PBMCs and ClC-7 knockdown bone marrow monocytes (BMMs) showed an enhanced Ser-71 phosphorylation of Rac1/Cdc42 and increase of the microphthalmia-associated transcription factor (MITF) and receptor activator of NF-κB (RANK) that can be responsible for the enhanced osteoclast differentiation. © 2018 The Authors. JBMR Plus published by Wiley Periodicals, Inc. on behalf of the American Society for Bone and Mineral Research.

Cavitation Damage Characteristics of Shot Peened ALBC3 Alloy.

Copper alloys have widely used for marine plants, ship building equipment, and renewable energy facilities under marine environment due to its excellent castability, durability, and corrosion resistance. In this study, the surface of ALBC3 alloy was modified with shot peening time to improve the strength and cavitation characteristics. For evaluation of cavitation resistance, cavitation experiments for the non-shot peened and shot-peened specimens were performed to investigate the extent of damage and determine the weight loss. As a result, the shot peened ALBC3 alloys improved cavitation resistance. In particular, the shot peening time of 3.5 min was considered to be the optimum shot peening condition since it presented an improvement of 35.7% in cavitation resistance.

Protein-Engineered Large Area Adipose-derived Stem Cell Sheets for Wound Healing.

Human adipose-derived stem cells (hADSCs) formed robust cell sheets by engineering the cells with soluble cell adhesive molecules (CAMs), which enabled unique approaches to harvest large area hADSC sheets. As a soluble CAM, fibronectin (FN) (100 pg/ml) enhanced the cell proliferation rate and control both cell-to-cell and cell-to-substrate interactions. Through this engineering of FN, a transferrable hADSC sheet was obtained as a free-stranding sheet (122.6 mm2) by a photothermal method. During the harvesting of hADSC sheets by the photothermal method, a collagen layer in-between cells and conductive polymer film (CP) was dissociated, to protect cells from direct exposure to a near infrared (NIR) source. The hADSC sheets were applied to chronic wound of genetically diabetic db/db mice in vivo, to accelerate 30% faster wound closure with a high closure effect (εwc) than that of control groups. These results indicated that the engineering of CAM and collagens allow hADSC sheet harvesting, which could be extended to engineer various stem cell sheets for efficient therapies.

Calcium-phosphate complex increased during subchondral bone remodeling affects earlystage osteoarthritis.

An activation of osteoclasts and subchondral bone remodeling is a major histologic feature of early-stage osteoarthritis (OA), which can be accompanied by an increase of calcium (Ca) and phosphate (Pi) level in the subchondral milieu. Considering articular cartilage gets most of nutrition from subchondral bone by diffusion, these micro-environmental changes in subchondral bone can affect the physiology of articular chondrocytes. Here, we have shown that Ca is increased and co-localized with Pi in articular cartilage of early-stage OA. The Ca-Pi complex increased the production of MMP-3 and MMP-13 in the hypertrophic chondrocytes, which was dependent on nuclear factor-kappa B (NF-kB), p38 and extracellular signal-regulated kinase (Erk) 1/2 mitogen-activated protein (MAP) kinase and Signal transducer and activator of transcription 3 (STAT3) signaling. The Ca-Pi complexes increased the expression of endocytosis markers, and the inhibition of the formation of the Ca-Pi complex ameliorated the Ca-Pi complex-mediated increases of MMPs expression in hypertrophic chondrocytes. Our data provide insight regarding the Ca-Pi complex as a potential catabolic mediator in the subchondral milieu and support the pathogenic role of subchondral bone in the early stages of cartilage degeneration.

Transparent Electrochemical Gratings from a Patterned Bistable Silver Mirror.

Silver mirror patterns were formed reversibly on a polystyrene (PS)-patterned electrode to produce gratings through the electrochemical reduction of silver ions. The electrochemical gratings exhibited high transparency (T > 95%), similar to a see-through window, by matching the refractive index of the grating pattern with the surrounding medium. The gratings switch to a diffractive state upon the formation of a mirror pattern (T < 5%) with a high diffraction efficiency up to 40%, providing reversible diffractive gratings. The diffraction state was maintained in the voltage-off state (V-off) for 40 min, which demonstrated bistable reversible electrochemical grating (BREG) behavior. By carefully combining the BREGs through period matching, dual-color switching was achieved within the full color region, which exhibited three distinct optical switching states between -2.5, 0, and +2.5 V. The wide range of light tenability using the metallic BREGs developed herein enabled IR modulation, NIR light reflection, and on-demand heat transfer.

Occurrence of Progressive Bone Loss Around Anodized Surface Implants and Resorbable Blasting Media Implants: A Retrospective Cohort Study.

BACKGROUND: This study evaluates occurrence of progressive bone loss (PBL) around implants with different implant surfaces. METHODS: Retrospective examination of 2,517 implants was performed in 903 patients, including 1,147 anodized-surface implants in 454 patients and 1,370 resorbable blasting media (RBM)-surface implants in 449 patients, which were placed from January 2006 to December 2010. Through regular check-up radiographs and records, presence of PBL (up to >50% of fixture length) was investigated. Implant removal for any reason was regarded a failure. RESULTS: In total, 2,186 implants (979 anodized implants and 1,207 RBM implants) in 793 patients were included in this study. PBL was more frequently observed among anodized implants (n = 36 in 21 patients; 4%) than among RBM implants (n = 19 in 14 patients; 2%), and this difference was statistically significant (P <0.001). Occurrence of PBL was significantly influenced by surface modification and implant diameter (odds ratio [OR] of anodized surface = 4.40, 95% confidence interval [CI] = 1.78 to 10.89, P = 0.001; OR of wide implants = 9.62, 95% CI = 1.13 to 81.68, P = 0.038; determined by mixed-effects logistic regression analysis with random patient effect). However, total survival rate was significantly influenced by implant diameter and not by surface modification (P = 0.019), although effect of implant diameter was observed to be significant on anodized implants (P = 0.030). CONCLUSION: Implant surface modification and implant diameter are significantly associated with occurrence of PBL.