Structure and gas transport characteristics of triethylene oxide-grafted polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene

Polymeric membrane-based gas separation technology has significant advantages compared with traditional amine-based CO₂ separation method. In this work, SEBS block copolymer is used as a polymer matrix to incorporate triethylene oxide (TEO) functionality. The short ethylene oxide segment is chosen to avoid crystallization, which is confirmed by differential scanning calorimetry and wide-angle X-ray scattering characterizations. The gas permeability results reveal that CO₂/N₂ selectivity increased with increasing content of TEO functional group. The highest CO₂ permeability (281 Barrer) and CO₂/N₂ selectivity (31) were obtained for the membrane with the highest TEO incorporation (57 mol%). Increasing the TEO content in these copolymers results in an increase in CO₂ solubility and a decrease in C₂H₆ solubility. For example, as the grafted TEO content increased from 0 to 57 mol%, the CO₂ solubility and CO₂/C₂H₆ solubility selectivity increased from 0.72 to 1.3 cm³(STP)/cm³ atm and 0.47 to 1.3 at 35°C, respectively. The polar ether linkage in TEO-grafted SEBS copolymers exhibits favorable interaction with CO₂ and unfavorable interaction with nonpolar C₂H₆, thus enhancing CO₂/C₂H₆ solubility selectivity.     

Increasing Chemical Diversity of B2N2 Anthracene Derivatives by Introducing Continuous Multiple Boron-Nitrogen Units

Increasing the chemical diversity of organic semiconductors is essential to develop efficient electronic devices. In particular, the replacement of carbon-carbon (C−C) bonds with isoelectronic boron-nitrogen (B−N) bonds allows precise modulation of the electronic properties of semiconductors without significant structural changes. Although some researchers have reported the preparation of B₂N₂ anthracene derivatives with two B−N bonds, no compounds with continuous multiple BN units have been prepared yet. Herein, we report the synthesis and characterization of a B₂N₂ anthracene derivative with a BNBN unit formed by converting the BOBN unit at the zigzag edge. Compared to the all-carbon analogue 2-phenylanthracene, BNBN anthracene exhibits significant variations in the C−C bond length and a larger highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap. The experimentally determined bond lengths and electronic properties of BNBN anthracene are confirmed through theoretical calculations. The BOBN anthracene organic light-emitting diode, used as a blue host, exhibits a low driving voltage. The findings of this study may facilitate the development of larger acenes with multiple BN units and potential applications in organic electronics.     

Human Albumin-Based Hydrogels for Their Potential Xeno-Free Microneedle Applications

Nowadays, hydrogels-based microneedles (MNs) have attracted a great interest owing to their outstanding qualities for biomedical applications. For the fabrication of hydrogels-based microneedles as tissue engineering scaffolds and drug delivery carriers, various biomaterials have been tested. They are required to feature tunable physiochemical properties, biodegradability, biocompatibility, nonimmunogenicity, high drug loading capacity, and sustained drug release. Among biomaterials, human proteins are the most ideal biomaterials for fabrication of hydrogels-based MNs; however, they are mechanically weak and poorly processible. To the best of the knowledge, there are no reports of xeno-free human protein-based MNs so far. Here, human albumin-based hydrogels and microneedles for tissue engineering and drug delivery by using relatively new processible human serum albumin methacryloyl (HSAMA) are engineered. The resultant HSAMA hydrogels display tunable mechanical properties, biodegradability, and good biocompatibility. Moreover, the xeno-free HSAMA microneedles display a sustained drug release profile and significant mechanical strength to penetrate the model skin. In vitro, they also show good biocompatibility and anticancer efficacy. Sustainable processible human albumin-based biomaterials may be employed as a xeno-free platform in vivo for tissue engineering and drug delivery in clinical trials in the future.     

β-TrCP1 degradation is a novel action mechanism of PI3K/mTOR inhibitors in triple-negative breast cancer cells

An F-box protein, β-TrCP recognizes substrate proteins and destabilizes them through ubiquitin-dependent proteolysis. It regulates the stability of diverse proteins and functions as either a tumor suppressor or an oncogene. Although the regulation by β-TrCP has been widely studied, the regulation of β-TrCP itself is not well understood yet. In this study, we found that the level of β-TrCP1 is downregulated by various protein kinase inhibitors in triple-negative breast cancer (TNBC) cells. A PI3K/mTOR inhibitor PI-103 reduced the level of β-TrCP1 in a wide range of TNBC cells in a proteasome-dependent manner. Concomitantly, the levels of c-Myc and cyclin E were also downregulated by PI-103. PI-103 reduced the phosphorylation of β-TrCP1 prior to its degradation. In addition, knockdown of β-TrCP1 inhibited the proliferation of TNBC cells. We further identified that pharmacological inhibition of mTORC2 was sufficient to reduce the β-TrCP1 and c-Myc levels. These results suggest that mTORC2 regulates the stability of β-TrCP1 in TNBC cells and targeting β-TrCP1 is a potential approach to treat human TNBC.     

Tuning the Redox Properties of a Nonheme Iron(III)–Peroxo Complex Binding Redox‐Inactive Zinc Ions by Water Molecules

Redox‐inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox‐inactive metal ions. The coordination of two water molecules to a Zn²⁺ ion in (TMC)Fe^III‐(O₂)‐Zn(CF₃SO₃)₂ ( 1 ‐Zn²⁺) decreases the Lewis acidity of the Zn²⁺ ion, resulting in the decrease of the one‐electron oxidation and reduction potentials of 1 ‐Zn²⁺. This further changes the reactivities of 1 ‐Zn²⁺ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1 ‐Zn²⁺, whereas 1 ‐Zn²⁺ coordinating two water molecules, (TMC)Fe^III‐(O₂)‐Zn(CF₃SO₃)₂‐(OH₂)₂ [ 1 ‐Zn²⁺‐(OH₂)₂], releases the O₂ unit in the oxidation reaction. In the reduction reactions, 1 ‐Zn²⁺ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1 ‐Zn²⁺‐(OH₂)₂. The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.     

Frenkel‐Defect‐Mediated Chemical Ordering Transition in a Li–Mn–Ni Spinel Oxide

Using spinel‐type Li(Mn_1.5Ni_0.5)O₄ with two different cations, Mn and Ni, in the oxygen octahedra as a model system, we show that a cation ordering transition takes place through the formation of Frenkel‐type point defects. A series of experimental results based on atomic‐scale observations and in situ powder diffractions along with ab initio calculations consistently support such defect‐mediated transition behavior. In addition to providing a precise suggestion of the intermediate transient states and the resulting kinetic pathway during the transition between two phases, our findings emphasize the significant role of point defects in ordering transformation of complex oxides.     

Direct Patterning and Biofunctionalization of a Large‐Area Pristine Graphene Sheet

Direct patterning of streptavidin and NIH 3T3 fibroblast cells was successfully achieved over a large‐area pristine graphene sheet on Si/SiO₂ by aryl azide‐based photografting with the conventional UV lithographic technique and surface‐initiated, atom transfer radical polymerization of oligo(ethylene glycol) methacrylate.     

Sulfated choline ionic liquid-catalyzed acetamide synthesis by grindstone method

Sulfated choline ionic liquid (SCIL) has been found to be an efficient solid acid IL catalyst for the protection of amine groups with acetic anhydride under solvent-free grindstone conditions. The attractive features of this new catalytic methodology include its sustainability, facile work-up procedure, economic viability, and biodegradability. The SCIL catalyst was characterized using infrared spectroscopy, wide-angle X-ray scattering analysis, and scanning electron microscopy with energy dispersive X-ray spectroscopy. The catalyst could be reused six times without significant loss in activity. Furthermore, no chromatographic separations were needed to obtain the desired products.     

Anti-Inflammatory Activity and Mechanism of Isookanin,Isolated by Bioassay-Guided Fractionation from Bidens pilosa L.

Bidens pilosa L. (Asteraceae) has been used historically in traditional Asian medicine and is known to have a variety of biological effects. However, the specific active compounds responsible for the individual pharmacological effects of Bidens pilosa L. (B. pilosa) extract have not yet been made clear. This study aimed to investigate the anti-inflammatory phytochemicals obtained from B. pilosa. We isolated a flavonoids-type phytochemical, isookanin, from B. pilosa through bioassay-guided fractionation based on its capacity to inhibit inflammation. Some of isookanin’s biological properties have been reported; however, the anti-inflammatory mechanism of isookanin has not yet been studied. In the present study, we evaluated the anti-inflammatory activities of isookanin using lipopolysaccharide (LPS)-stimulated RAW 264.7 macrophages. We have shown that isookanin reduces the production of proinflammatory mediators (nitric oxide, prostaglandin E₂) by inhibiting the expression of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) in LPS-stimulated macrophages. Isookanin also inhibited the expression of activator protein 1 (AP-1) and downregulated the LPS-induced phosphorylation of p38 mitogen-activated protein kinase (MAPK) and c-jun NH₂-terminal kinase (JNK) in the MAPK signaling pathway. Additionally, isookanin inhibited proinflammatory cytokines (tumor necrosis factor-a (TNF-α), interleukin-6 (IL-6), interleukin-8 (IL-8), and interleukin-1β (IL-1β)) in LPS-induced THP-1 cells. These results demonstrate that isookanin could be a potential therapeutic candidate for inflammatory disease.