ABSTRACT
This work shows that hollow Ru/RuO2 nanoparticles having nanoparticulate shells (HN-Ru/RuO2) can be prepared using hollow microporous organic polymers with Ru species (H-MOP-Ru) as precursors. Using silica spheres as templates, H-MOPs were prepared through the Sonogashira-Hagihara coupling of 1,3,5-triethynylbenzene with 2,3-ethoxymethylenedioxy-1,4-diiodobenzene. Acid hydrolysis of cyclic ethyl orthoformate protecting groups generated catechol moieties to form H-MOP-Cat. Then, H-MOP-Ru was obtained by incorporating Ru species into H-MOP-Cat. Heat-treatment of H-MOP-Ru under air induced the formation of HN-Ru/RuO2 with a diameter of 61 nm and shells consisting of 6-7 nm nanoparticles. Due to the hollow structure and nanoparticulate shells, HN-Ru/RuO2 showed a high surface area of 80 m2 g-1 and a pore volume of 0.18 cm3 g-1. The HN-Ru/RuO2 showed enhanced electrocatalytic performance for the oxygen evolution reaction (OER) with an overpotential of 295 mV @ 10 mA cm-2 and a Tafel slope of 46 mV dec-1 in alkaline electrolyte, compared with control RuO2 such as commercial Ru/RuO2 nanoparticles (A-Ru/RuO2) and home-made Ru/RuO2 nanoparticles (N-Ru/RuO2) prepared via the same synthetic procedure as HN-Ru/RuO2. While HN-Ru/RuO2 inevitably contained Pd originated from coupling catalysts, it showed superior performance to Ru/RuO2 nanoparticles with the same Pd content (N1-Ru/RuO2), indicating that the efficient electrocatalytic performance of HN-Ru/RuO2 is attributable to its hollow structure and nanoparticulate shells.
ABSTRACT
The demand for lithium-ion batteries (LIBs) has increased rapidly. However, commercial inorganic-based cathode materials have a low theoretical capacity and inherent disadvantages, such as high cost and toxicity. Redox-active organic cathodes with a high theoretical capacity, eco-friendly properties, and sustainability have been developed to overcome these limitations. Herein, perylene diimide derivatives N-substituted with 1,2,4-triazol-3-yl rings (PDI-3AT) were developed to apply as a cathode material for LIBs. The PDI-3AT cathode exhibited discharge capacities of 85.2 mAh g-1 (50 mA g-1 over 100 cycles) and 64.5 mAh g-1 (500 mA g-1 over 1000 cycles) with ratios to the theoretical capacities of 84 and 64%, respectively. Electrochemical kinetics analysis showed capacitive behaviors of the PDI-3AT cathode with efficient pathways for lithium-ion transport. Also, the activation step of the PDI-3AT cathode was demonstrated by improving the charge transfer resistance and lithium-ion diffusion coefficient during the initial few charge-discharge cycles. Furthermore, DFT calculations at the B3LYP/6-311+G** level and ex situ analysis of various charge states of the PDI-3AT electrode using attenuated total reflection Fourier transform infrared (ATR FT-IR) analysis, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were conducted for the further study of the lithium-ion storage mechanism. The results showed that the lithiation process formed the lithium enolate (âC-O-Li) coordinated with the N atoms of the 1,2,4-triazole ring. It is expected that our study results will encourage the production and use of redox-active perylene diimide derivatives as next-generation cathode materials.
ABSTRACT
Dahl Salt-Sensitive (DSS) rats develop heart failure with preserved ejection fraction (HFpEF) when fed a high-salt (8 % NaCl) diet. Hypertension-induced inflammation and subsequent ventricular fibrosis are believed to underlie the development of HFpEF. We investigated the role of diet modification in the progression of HFpEF using male DSS rats, fed either a high-salt diet from7 weeks of age to induce HFpEF, ora normal-salt (0.3% NaCl) diet as controls. After echocardiographic confirmation of diastolic dysfunction at 14-15 weeks of age along with HF manifestations, the HFpEF rats were randomly assigned to either continue a high-salt diet or switch to a normal-salt diet for an additional 4 weeks. HFpEF rats with diet modification showed improved diastolic function (reduced E/E' ratio in echocardiogram), increased functional capacity (increased treadmill exercise distance), and reduced pulmonary congestions (lung/body weight ratio), compared to high-salt-fed HFpEF rats. Systolic blood pressure remained high (~200 mmHg), and ventricular hypertrophy remained unchanged. Ventricular arrhythmia inducibility (100 % inducible) and corrected QT interval (on ECG) did not change in HFpEF rats after diet modification. HFpEF rats with diet modification showed prolonged survival and reduced ventricular fibrosis (Masson's trichrome staining) compared to high-salt-fed HFpEF rats. Hence, the modification of diet (from high-salt to normal-salt diet) reversed HFpEF phenotypes without affecting blood pressure or ventricular hypertrophy.
ABSTRACT
The radial forearm free flap (RFFF) has become popular for head and neck reconstructions. Owing to a constant anatomy the RFFF is relatively easy to dissect. Nevertheless, anatomical variations of the radial artery have been reported. Some variations could affect the survival of the flap. This paper reports an unusual anomaly of the radial artery where the radial artery was not located between the brachioradialis (BR) and flexor carpi radialis. The radial artery was observed above the BR and on the radial side of the BR. The survival of the elevated flap was deemed questionable because it had only few perforators. So we decided to discard the flap and to elevate another free flap for the head and neck defect. The donor area on the forearm was covered using the original skin of the first flap as a full-thickness skin graft. This case highlights a means to deal with anomalies of the radial artery encountered during the elevation of RFFF and the checking process for variations of the radial artery before RFFF.
ABSTRACT
Background@#Conventional radial forearm free flaps (RFFFs) are known to be safe, but can result in donor site complications. Based on our experiences with suprafascial and subfascial RFFFs, we evaluated the safety of flap survival and surgical outcomes. @*Methods@#This was a retrospective study of head and neck reconstructions using RFFFs from 2006 to 2021. Thirty-two patients underwent procedures using either subfascial (group A) or suprafascial (group B) dissection for flap elevation. Data were collected on patient characteristics, flap size, and donor and recipient complications, and the two groups were compared. @*Results@#Thirteen of the 32 patients were in group A and 19 were in group B. Group A included 10 men and three women, with a mean age of 56.15 years, and group B included 16 men and three women, with a mean age of 59.11 years. The mean defect areas were 42.83 cm² and 33.32 cm², and the mean flap sizes were 50.96 cm² and 44.54 cm² in groups A and B, respectively. There were 13 donor site complications: eight (61.5%) in group A and five (26.3%) in group B. Flexor tendon exposure occurred in three patients in group A and in none in group B. All flaps survived completely. A recipient site complication occurred in two patients (15.4%) in group A and three patients (15.8%) in group B. @*Conclusions@#Complications and flap survival were similar between the two groups. However, tendon exposure at the donor site was less prevalent in the suprafascial group, and the treatment period was shorter. Based on our data, suprafascial RFFF is a reliable and safe procedure for reconstruction of the head and neck.
ABSTRACT
For the successful clinical advancement of exosome therapeutics, the biodistribution and pharmacokinetic profile of exogenous exosomes in various animal models must be determined. Compared with fluorescence or bioluminescence imaging, radionuclide imaging confers multiple advantages for the in vivo tracking of biomolecular therapeutics because of its excellent sensitivity for deep tissue imaging and potential for quantitative measurement. Herein, we assessed the quantitative biodistribution and pharmacokinetics of good manufacturing practice-grade therapeutic exosomes labeled with zirconium-89 (89Zr) after systemic intravenous administration in mice and rats. Quantitative biodistribution analysis by positron emission tomography/computed tomography and gamma counting in mice and rats revealed that the total 89Zr signals in the organs were lower in rats than in mice, suggesting a higher excretion rate of exosomes in rats. A prolonged 89Zr signal for up to 7 days in most organs indicated that substantial amounts of exosomes were taken up by the parenchymal cells in those organs, highlighting the therapeutic potential of exosomes for the intracellular delivery of therapeutics. Exosomes were mainly distributed in the liver and to a lesser extent in the spleen, while a moderately distributed in the kidney, lung, stomach, intestine, urinary bladder, brain, and heart. Exosomes were rapidly cleared from the blood circulation, with a rate greater than that of free 89Zr, indicating that exosomes might be rapidly taken up by cells and tissues.
ABSTRACT
The one-pot synthesis process has emerged as an economical synthesis method without the involvement of purification or formation of intermediate compounds. Therefore, nickel nanoparticles were selectively synthesized by a simple hydrothermal method using nickel(II) chloride hexahydrate and borane-ammonia complex as a precursor and reducing agent, respectively. The morphology and crystal growth were observed by controlling the precursor concentration ratio of Ni:AB from 1:0.1 to 1:4 under various temperatures ranging from 80 to 140 degrees. In addition, we observed that the crystal growth rate under the influence of NaCl and KCl resulted in spherical Ni particles with size distributions controlled in the range of 297.65 nm to 1082.15 nm and 358.6 nm to 605 nm, respectively.
ABSTRACT
Bilateral pectoralis major myocutaneous (PMMC) flaps are commonly used to reconstruct large chest wall defects. We report a case of large chest wall defect reconstruction using bilateral PMMC flaps augmented with axillary V-Y advancement rotation flaps for additional flap advancement. A 74-year-old male patient was operated on for recurrent glottic squamous cell carcinoma. Excision of the tumor resulted in a 10×10 cm defect in the anterior chest wall. Bilateral PMMC flaps were raised to cover the chest wall defect. For further flap advancement, V-Y rotation advancement flaps from both axillae were added to allow complete closure. All flaps survived completely, and postoperative shoulder abduction was not limited (100° on the right side and 92° on the left). Age-related skin redundancy in the axillae enabled the use of V-Y rotation advancement flaps without limitation of shoulder motion. Bilateral PMMC advancement flaps and the additional use of V-Y rotation advancement flaps from both axillae may be a useful reconstructive option for very large chest wall defects in older patients.
ABSTRACT
Sodium ion batteries (SIBs) have drawn interest as a lithium ion battery (LIB) alternative owing to their low price and low deposits. To commercialize SIBs similar to how LIBs already have been, it is necessary to develop improved anode materials that have high stability and capacity to operate over many and long cycles. This paper reports the development of homogeneous Sb2S3 nanorods (Sb2S3 NRs) on reduced graphene oxide (Sb2S3 NRs @rGO) as anode materials for SIBs. Based on this work, Sb2S3 NRs show a discharge capacity of 564.42 mAh/g at 100 mA/g current density after 100 cycles. In developing a composite with reduced graphene oxide, Sb2S3 NRs@rGO present better cycling performance with a discharge capacity of 769.05 mAh/g at the same condition. This achievement justifies the importance of developing Sb2S3 NRs and Sb2S3 NRs@rGO for SIBs.
ABSTRACT
A microporous organic polymer (MOP) was utilized for the engineering of nanoparticulate CeO2 in a hollow carbon matrix (H-C/CeO2). After CeO2 nanoparticles were incorporated into a hollow MOP platform (H-MOP) through the decomposition of cerium acetate, successive carbonization produced H-C/CeO2. The redox feature of defective CeO2 in a conductive carbon matrix induced promising pseudocapacitive behavior. In particular, the H-C/CeO2 showed excellent electrochemical performance in an alkaline electrolyte (KOH), due to the hydroxide ion-assisted redox behavior of defective CeO2. H-C/CeO2-3 with an optimized amount of CeO2 showed specific capacitances of up to 527 (@0.5 A g-1) and 493 F g-1 (@1 A g-1). Even at high current densities of 10 and 20 A g-1, the H-C/CeO2-3 maintained high capacitances of 458 and 440 F g-1, respectively. After 10 000 cycling tests, the H-C/CeO2-3 retained the 94-95% capacitance of the first cycle.
ABSTRACT
Lithium batteries that utilize a lithium anode and a high voltage cathode are highly required to meet the growing demand for electrification of transportation. High voltage lithium cobalt oxide (LiCoO2, LCO) can be a promising choice for lithium batteries with high energy and power. However, intrinsic structural instability at high voltages (>4.2 V) leads to significant capacity loss during the repeated cycles of charge-discharge. Herein, a simple and effective method has been proposed to prepare an artificial protective layer of LCO, enabling the LCO to achieve long-term cycle stability at 4.5 V. It is found that carbon monofluoride reacts with LCO via defluorination at 400 °C to form a LiF-C layer on LCO, which suppresses side reactions at the electrolyte/electrode interface. Moreover, the LiF-C layer plays a key role in not only facilitating charge transport but also restricting Co dissolution from the cathode. The Li//LiF-C coated LCO cells deliver an initial discharge capacity of 186 mAh g-1 at 0.1C and exhibit excellent cycling and rate performance: 161 mAh g-1 after 180 cycles (90% of the initial value at 0.5C) and 115 mAh g-1 at 10C (63.2% of the 0.1C capacity).
ABSTRACT
Ischemia-reperfusion injury is a major cause of acute kidney injury. Recent studies on the pathophysiology of ischemia-reperfusion-induced acute kidney injury showed that immunologic responses significantly affect kidney ischemia-reperfusion injury and repair. Nuclear factor (NF)-ĸB signaling, which controls cytokine production and cell survival, is significantly involved in ischemia-reperfusion-induced acute kidney injury, and its inhibition can ameliorate ischemic acute kidney injury. Using EXPLOR, a novel, optogenetically engineered exosome technology, we successfully delivered the exosomal super-repressor inhibitor of NF-ĸB (Exo-srIĸB) into B6 wild type mice before/after kidney ischemia-reperfusion surgery, and compared outcomes with those of a control exosome (Exo-Naïve)-injected group. Exo-srIĸB treatment resulted in lower levels of serum blood urea nitrogen, creatinine, and neutrophil gelatinase-associated lipocalin in post-ischemic mice than in the Exo-Naïve treatment group. Systemic delivery of Exo-srIĸB decreased NF-ĸB activity in post-ischemic kidneys and reduced apoptosis. Post-ischemic kidneys showed decreased gene expression of pro-inflammatory cytokines and adhesion molecules with Exo-srIĸB treatment as compared with the control. Intravital imaging confirmed the uptake of exosomes in neutrophils and macrophages. Exo-srIĸB treatment also significantly affected post-ischemic kidney immune cell populations, lowering neutrophil, monocyte/macrophage, and T cell frequencies than those in the control. Thus, modulation of NF-ĸB signaling through exosomal delivery can be used as a novel therapeutic method for ischemia-reperfusion-induced acute kidney injury.
Subject(s)
Acute Kidney Injury , Exosomes , Reperfusion Injury , Acute Kidney Injury/etiology , Acute Kidney Injury/prevention & control , Animals , Kidney , Mice , Mice, Inbred C57BL , NF-KappaB Inhibitor alpha , Reperfusion Injury/prevention & controlABSTRACT
In lithium metal batteries (LMBs), electrolytes composed of salts and organic solvents play a significant role in transporting Li+ ions and creating the surface film on Li-metal anodes. Herein, the effect of methyl acetate (MA) as a co-solvent is reported, which enables the facilitated Li+ transport and formation of a robust solid electrolyte interphase (SEI) on the Li-metal anode. The symmetrical Li//Li cell tests show remarkable cycle stability of MA-based electrolytes at 3 mA/cm2 without obvious voltage fluctuation. At 5 mA/cm2, the Li//Li cells in MA-based electrolytes can still run up to 110 h with lower overpotential, compared to the cell cycled with MA-free electrolytes. Furthermore, the LMBs consisting of the Li anode and LiNi0.8Co0.15Al0.05O2 (NCA) cathode deliver the high capacity (â¼200 mA h/g), good cycling stability up to 300 cycles, excellent rate capability (10 C), and low self-discharging rates (8.5%) with MA-based electrolytes. Especially, the capacity of the Li//NCA cells with MA30 electrolytes at -35 °C is as high as 144 mA h/g, which is higher than that of the cells in MA-free electrolytes. It demonstrates that the MA is beneficial for the LMB operation at high rate and low temperature.
ABSTRACT
The so-called colloidal template synthesis has been applied to the preparation of surface-engineered nanoadsorbents. Colloidal microporous organic network nanotemplates (C-MONs), which showed a high surface area (611â m2 g-1 ) and enhanced microporosity, were prepared through the networking of organic building blocks in the presence of poly(vinylpyrrolidone) (PVP). Owing to entrapment of the PVP in networks, the C-MONs showed good colloidal dispersion in EtOH. MoS2 precursors were incorporated into the C-MONs and heat treatment afforded core-shell-type C@MoS2 nanoparticles with a diameter of 80â nm, a negative zeta potential (-39.5â mV), a high surface area (508â m2 g-1 ), and excellent adsorption performance towards cationic dyes (qmax =343.6 and 421.9â mg g-1 for methylene blue and rhodamineâ B, respectively).
ABSTRACT
Lattice matching has been supposed to play an important role in the coupling between two materials in a vertical heterostructure (HS). To investigate this role, we fabricated a heterojunction device with a few layers of p-type WSe2 and n-type MoSe2 with different crystal orientation angles. The crystal orientations of WSe2 and MoSe2 were estimated using high-resolution X-ray diffraction. Heterojunction devices were fabricated with twist angles of 0, 15, and 30°. The I- V curve of the sample with the twist angle of 0° under the dark condition showed a diodelike behavior. The strong coupling due to lattice matching caused a well-established p-n junction. In cases of 15 and 30° samples, the van der Waals gap was built because of lattice mismatching, which resulted in the formation of a potential barrier. However, when the light-emitting diode light of 365 nm (3.4 eV) was illuminated, it was possible for excited electrons and holes to jump beyond the potential barrier and the current flowed well in both forward and reverse directions. The effects of the twist angle were analyzed by spectral responsivity and external quantum efficiency, where it was found that the untwisted HS exhibited higher sensitivity under IR illumination, whereas the twisting effect was not noticeable under UV illumination. From photoluminescence and Raman spectroscopy studies, it was confirmed that the twisted HS showed a weak coupling because of the lattice mismatch.
ABSTRACT
Photocatalytic water splitting is a vital technology for clean renewable energy. Despite enormous progress, the search for earth-abundant photocatalysts with long-term stability and high catalytic activity is still an important issue. We report three possible polymorphs of nickel selenide (orthorhombic phase NiSe2, cubic phase NiSe2, and hexagonal phase NiSe) as bifunctional catalysts for water-splitting photoelectrochemical (PEC) cells. Photocathodes or photoanodes were fabricated by depositing the nickel selenide nanocrystals (NCs) onto p- or n-type Si nanowire arrays. Detailed structural analysis reveals that compared to the other two types, the orthorhombic NiSe2 NCs are more metallic and form less surface oxides. As a result, the orthorhombic NiSe2 NCs significantly enhanced the performance of water-splitting PEC cells by increasing the photocurrents and shifting the onset potentials. The high photocurrent is ascribed to the excellent catalytic activity toward water splitting, resulting in a low charge-transfer resistance. The onset potential shift can be determined by the shift of the flat-band potential. A large band bending occurs at the electrolyte interface, so that photoelectrons or photoholes are efficiently generated to accelerate the photocatalytic reaction at the active sites of orthorhombic NiSe2. The remarkable bifunctional photocatalytic activity of orthorhombic NiSe2 promises efficient PEC water splitting.
ABSTRACT
This work shows that the functions of microporous organic network materials can be enhanced through engineering of the material structure. Mimicking the surface structure of velvet worms, we prepared the aligned 1D structure (rod) of microporous porphyrin networks by the Sonogashira coupling of tetrakis(4-ethynylphenyl)porphyrin with 1,4-diiodobenzene in an anodic aluminum oxide plate. The length of the 1D structure was controlled in the range of 1-5 µm. The velvet worm surface-like microporous porphyrin networks (Velvet-MPNs) showed higher sensitivities to hydrogen chloride and ammonia gases by up to â¼14 and 4.6 times, respectively, compared with a control MPN material without rods.
Subject(s)
Porphyrins/chemistry , Aluminum Oxide , Ammonia , Gases , Hydrochloric AcidABSTRACT
Cation substitution of Bi3+ with Fe3+ in BiOCl leads to the formation of ionically layered Bi0.7Fe0.3OCl nanosheets. The synthesis follows a hydrolysis route using bismuth(III) nitrate and iron(III) chloride, followed by postannealing at 500 °C. Room temperature electrical conductivity improves from 6.11 × 10-8 S/m for BiOCl to 6.80 × 10-7 S/m for Bi0.7Fe0.3OCl. Correspondingly, the activation energy for electrical conduction reduces from 862 meV for pure BiOCl to 310 meV for Bi0.7Fe0.3OCl. These data suggest improved charge mobility in Bi0.7Fe0.3OCl nanosheets. Density functional theory calculations confirm this behavior by predicting a high density of states near the Fermi level for Bi0.7Fe0.3OCl. The improvement in electrical conductivity is exploited in the electrochemical performance of Bi0.7Fe0.3OCl nanosheets. The insertion capacity of Li+ ions shows an increase of 2.5×, from 215 mAh·.g-1 for undoped BiOCl to 542 mAh·g-1 for Bi0.7Fe0.3OCl after 50 cycles at a current density of 50 mA·g-1. Thus, the direct substitution of Bi3+ sites with Fe3+ in BiOCl results in nanosheets of an ionically layered ternary semiconductor compound which is attractive for Li ion battery anode applications.
ABSTRACT
Yolk-shell-type polystyrene@microporous organic network (Y-PS@MON) materials were prepared by the Sonogashira coupling of tetra(4-ethynylphenyl)methane and 1,4-diiodobenzene on the surface of PS@SiO2 and by the etching of SiO2. The diameter of PS yolk spheres and the thickness of MON shells were 150 and â¼10 nm, respectively. The thickness of the void space between the PS yolk and the MON shell was â¼30 nm. Y-PS@MONs were used as templates for the synthesis of MoS2/C composite materials. Because of the microporosity of the MON shells and the void space between the yolk and the shell, MoS2 precursor compounds were efficiently incorporated into Y-PS@MONs. The heat treatment under argon resulted in the formation of hollow MoS2/C composites. The contents of MoS2 in the composites were systematically controlled by changing the amounts of precursor. MoS2/C with 58 wt % of MoS2 showed the best energy storage performance with a capacitance of 418 F/g at a 0.5 A/g current density as an electrode material of a coin cell supercapacitor, which is attributable to its hollow structure, high surface area, and the good distribution of the sliced MoS2 in the carbon matrix. Also, the MoS2/C-58 composite showed excellent retention of capacitances during 5000 cycles.
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A glucose-responsive closed-loop insulin delivery system represents an ideal form of treatment for type 1 diabetes mellitus. Here, we develop a glucose-responsive protein delivery system based on chitosan microgels loaded with enzyme-mimicking inorganic nanoparticles. The pH-sensitive chitosan microgels, integrated with glucose-mediated pH-lowering enzymatic large-pore mesoporous silica (MCF), were fabricated via an electrospray process. Ceria nanoparticles (CeNPs), which is a catalase-mimicking inorganic artificial enzyme with a substantial stability compared to that of catalase, were incorporated into the MCF along with glucose oxidase. In hyperglycemic conditions, CeNPs successfully decomposed the toxic hydrogen peroxide that was generated from the glucose oxidation reaction mediated by glucose oxidase and regenerate oxygen; this protected glucose oxidase from denaturation. The pH-lowering induced by the enzymatic MCF in high glucose concentration resulted in swelling of the chitosan microgels and the subsequent release of the encapsulated model protein drug, such as bovine serum albumin and insulin. Finally, we successfully demonstrated self-regulated repetitive protein release from the chitosan microgels, which showed a basal release rate under normoglycemic conditions and an enhanced release rate under hyperglycemic conditions.