Superior Charge Transport in Ni-Diamine Conductive MOFs.

Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm-1, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications. When such high conductivities are achieved, Ni-diamine linkages are often involved, yet Ni-diamine MOFs remain difficult to access. Here, we report two new 2D cMOFs made through ortho-diamine connections: M3(HITT)2 (M = Ni, Cu; HITT = 2,3,7,8,12,13-hexaiminotetraazanaphthotetraphene). The electrical conductivity of Ni3(HITT)2 reaches 4.5 S cm-1 at 298 K, whereas the conductivity of Cu3(HITT)2 spans from 0.05 (2Cu+Cu2+) to 10-6 (3Cu2+) upon air oxidation, much lower than that of Ni3(HITT)2. Spectroscopic analysis reveals that Ni3(HITT)2 exhibits significantly stronger in-plane π-d conjugation and higher density of charge carriers compared to Cu3(HITT)2, accounting for the higher electrical conductivity of Ni3(HITT)2. Cu2+/Cu+ mixed valency modulates the energy level and carrier density of Cu3(HITT)2, allowing for a variation of electrical conductivity over 4 orders of magnitude. This work provides a deeper understanding of the influence of metal nodes on electrical conductivity and confirms ortho-diamine linkers as privileged among ligands for 2D cMOFs.

Anti-inflammatory potential of Lactobacillus reuteri LM1071 via eicosanoid regulation in LPS-stimulated RAW264.7 cells.

AIMS: To investigate anti-inflammatory effects of Lactobacillus reuteri LM1071 in lipopolysaccharides (LPS)-induced inflammation RAW264.7 cells. METHODS AND RESULTS: To evaluate anti-inflammatory activities of L. reuteri LM1071, LPS-stimulated RAW264.7 cells were used. Gene expression levels of eight immune-associated genes including IL-1ß, IL-6 and TNF-α and protein production levels of COX-1 and COX-2 were analysed. Moreover, the production of eicosanoids as important biomarkers for anti-inflammation was determined. CONCLUSIONS: The current study demonstrates that L. reuteri LM1071 has anti-inflammatory potential by inhibiting the production of inflammation mediators such as NO, eicosanoids such as PGE1 & PGE2, pro-inflammatory cytokines and COX proteins. It can also enhance the production of inflammatory associated genes such as IL-11, BMP4, LEFTY2 and EET metabolite. SIGNIFICANCE AND IMPACT OF THE STUDY: Lactobacillus reuteri is one of the crucial bacteria for food fermentation. It can be found in the gastrointestinal system of human and animals. Several studies have shown that L. reuteri has valuable effects on host health. The current study firstly demonstrated that L. reuteri has a beneficial effect on the inflammation containing the variation of eicosanoids (PGE1 and PGE2) which are one of the most important biomarkers and moreover eicosanoid-associated genes as well as proteins (COX-2).

Density Functional Theory Study of Synergistic Gas Sensing Using an Electrically Conductive Mixed Ligand Two-Dimensional Metal-Organic Framework.

Two-dimensional conductive metal-organic frameworks (2D-cMOFs) have been adopted in electrochemical sensing applications owing to their superior electrical conductivity and large surface area. Here, we performed a density functional theory (DFT) analysis to study the synergistic impact of introducing a secondary organic ligand to the 2D-cMOF system. In this study, cobalt-hexaiminobenzene (Co-HIB) and cobalt-2,3,6,7,10,11-hexaiminotriphenylene (Co-HITP) were combined to form a mixed ligand MOF named, Co-HIB-HITP. A DFT-level comparative study was designed to access stability, synergistic gas adsorption capability, and gas adsorption mechanism, important factors in sensing material development. A potential energy surface calculation predicted the structural stability of Co-HIB-HITP at larger interlayer displacements around 3.6-4.2 Å regions along the ab-plane than its unmixed states, Co-HIB and Co-HITP, indicating the tunability of the stacking mode using the mixed ligand system. Furthermore, the adsorption capabilities toward toxic gases, NH3, H2S, NO, and NO2, were investigated, and Co-HIB-HITP revealed superiority over unmixed 2D-cMOFs in H2S and NH3 gas adsorption energies by showing 158 and 170% improvement, respectively. Finally, an electron charge density analysis revealed Co-HIB-HITP's unique stacking mode and Co-metal density as contributing factors to its gas-selective synergy effect. The AB stacked layers and an intermediate metal density (5.25%) significantly improved the electrostatic interactions with H2S and NH3 by inducing a change in the chemical environment of the gas binding sites. This work proposes the dual-ligand 2D-cMOF as the promising design strategy for the next-generation sensing material.

Effect of steric hindrance on the interfacial connection of MOF-on-MOF architectures.

MOF-on-MOF is attracting great attention due to its improved and/or synergistic properties not exhibited in a single MOF. In particular, the non-isostructural pairs of MOF-on-MOFs can have great potential induced by large heterogeneity, which enables diverse applications in a wide range of fields. HKUST-1@IRMOF is a fascinating platform because the alteration of the IRMOF pores with bulkier substituent groups on the ligands can provide a more microporous environment. However, the sterically hindered linker can affect the seamless growth at the interface, an important issue in practical research fields. Despite many efforts to reveal the growth of a MOF-on-MOF, there is still a lack of studies on a MOF-on-MOF consisting of a sterically hindered interface. Indeed, the effect of a bulky linker at an interface of HKUST-1@IRMOF, a non-isostructural MOF-on-MOF system, has not yet been reported, and thus, how the interfacial strain affects the interfacial growth remains unknown. In this study, we investigate the effect of an interfacial strain on a chemical connection point in an MOF-on-MOF system through a series of theoretical and synthetic experiments using a HKUST-1@IRMOF system. Our results reveal the importance of the proximity of each coordinating site at a MOF-on-MOF interface as well as lattice parameter matching for an effective secondary growth to achieve a well-connected MOF-on-MOF.

Computational Prediction of Stacking Mode in Conductive Two-Dimensional Metal-Organic Frameworks: An Exploration of Chemical and Electrical Property Changes.

Conductive two-dimensional metal-organic frameworks (2D MOFs) have attracted interest as they induce strong charge delocalization and improve charge carrier mobility and concentration. However, characterizing their stacking mode depends on expensive and time-consuming experimental measurements. Here, we construct a potential energy surface (PES) map database for 36 2D MOFs using density functional theory (DFT) for the experimentally synthesized and non-synthesized 2D MOFs to predict their stacking mode. The DFT PES results successfully predict the experimentally synthesized stacking mode with an accuracy of 92.9% and explain the coexistence mechanism of dual stacking modes in a single compound. Furthermore, we analyze the chemical (i.e., host-guest interaction) and electrical (i.e., electronic structure) property changes affected by stacking mode. The DFT results show that the host-guest interaction can be enhanced by the transition from AA to AB stacking, taking H2S gas as a case study. The electronic band structure calculation confirms that as AB stacking displacement increases, the in-plane charge transport pathway is reduced while the out-of-plane charge transport pathway is maintained or even increased. These results indicate that there is a trade-off between chemical and electrical properties in accordance with the stacking mode.

Ultrasensitive Near-Infrared InAs Colloidal Quantum Dot-ZnON Hybrid Phototransistor Based on a Gradated Band Structure.

Amorphous metal oxide semiconductor phototransistors (MOTPs) integrated with colloidal quantum dots (QDs) (QD-MOTPs) are promising infrared photodetectors owing to their high photoconductive gain, low off-current level, and high compatibility with pixel circuits. However, to date, the poor mobility of conventional MOTPs, such as indium gallium zinc oxide (IGZO), and the toxicity of lead (Pb)-based QDs, such as lead sulfide and lead selenide, has limited the commercial applications of QD-MOTPs. Herein, an ultrasensitive QD-MOTP fabricated by integrating a high-mobility zinc oxynitride (ZnON)-based MOTP and lead-free indium arsenide (InAs) QDs is demonstrated. A new gradated bandgap structure is introduced in the InAs QD layer that absorbs infrared light, which prevents carriers from moving backward and effectively reduces electron-hole recombination. Chemical, optical, and structural analyses confirm the movement of the photoexcited carriers in the graded band structure. The novel QD-MOTP exhibits an outstanding performance with a responsivity of 1.15 × 105 A W-1 and detectivity of 5.32 × 1016 Jones at a light power density of 2 µW cm-2 under illumination at 905 nm.

Short-chain fluorocarbon-based polymeric coating with excellent nonwetting ability against chemical warfare agents.

The ongoing concerns and regulations on long-chain fluorinated compounds (C8 or higher) for nonwetting coatings have driven the market to search for sustainable alternative chemistries. In this study, a copolymeric coating containing short-chain fluorinated groups was synthesized to achieve excellent nonwetting ability against hazardous chemical warfare agents (CWAs). A copolymer of 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) and ethylene glycol dimethacrylate (EGDMA, crosslinker) was directly coated onto a textile fabric via initiated chemical vapor deposition. The p(PFOMA-co-EGDMA) coating shows a rough-textured morphology with a bumpy, raspberry-like structure leading to high contact angles (θ water > 150° and θ dodecane = 113.8°) and a small water shedding angle (<5°). Moreover, the p(PFOMA-co-EGDMA) coating was further analysed for application in military fabrics: air permeability, tensile strength, and safety against toxic perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Outstanding nonwetting was noticeably achieved against different CWAs, including bis(2-chloroethyl)sulfide (HD), pinacolyl methylfluorophosphonate (GD), and O-ethyl S-(2-diisopropylaminoethyl)methylphosphonothioate (VX) (θ HD = 119.1°, θ GD = 117.0°, and θ VX = 104.1°). The coating retained its nano-structuration and nonwetting ability for water and n-dodecane despite being subjected to 250 cycles of Martindale abrasion and harsh chemicals (NaOH and HCl). The robustness and scalable straightforward preparation route of the coating make it an ideal approach for designing durable next-generation CWA nonwetting coatings for fabrics with favorable health and environmental properties.

Blockade of translationally controlled tumor protein attenuated the aggressiveness of fibroblast-like synoviocytes and ameliorated collagen-induced arthritis.

Histamine releasing factor/translationally controlled tumor protein (HRF/TCTP) stimulates cancer progression and allergic responses, but the role of HRF/TCTP in rheumatoid arthritis (RA) remains undefined. In this study, we explored the pathogenic significance of HRF/TCTP and evaluated the therapeutic effects of HRF/TCTP blockade in RA. HRF/TCTP transgenic (TG) and knockdown (KD) mice with collagen-induced arthritis (CIA) were used to determine the experimental phenotypes of RA. HRF/TCTP levels in the sera of RA patients were measured and compared to those from patients with osteoarthritis (OA), ankylosing spondylitis, Behçet's disease, and healthy controls. HRF/TCTP expression was also assessed in the synovium and fibroblast-like synoviocytes (FLSs) obtained from RA or OA patients. Finally, we assessed the effects of HRF/TCTP and dimerized HRF/TCTP-binding peptide-2 (dTBP2), an HRF/TCTP inhibitor, in RA-FLSs and CIA mice. Our clinical, radiological, histological, and biochemical analyses indicate that inflammatory responses and joint destruction were increased in HRF/TCTP TG mice and decreased in KD mice compared to wild-type littermates. HRF/TCTP levels in the sera, synovial fluid, synovium, and FLSs were higher in patients with RA than in control groups. Serum levels of HRF/TCTP correlated well with RA disease activity. The tumor-like aggressiveness of RA-FLSs was exacerbated by HRF/TCTP stimulation and ameliorated by dTBP2 treatment. dTBP2 exerted protective and therapeutic effects in CIA mice and had no detrimental effects in a murine tuberculosis model. Our results indicate that HRF/TCTP is a novel biomarker and therapeutic target for the diagnosis and treatment of RA.

Surface-Modified Filter-Based Continuous Recovery of Microalgal Lipid-in-Solvent with High Recovery Efficiency, Long-Term Stability, and Cost Competitiveness.

Microalgal lipid-derived biofuels have been regarded as promising candidate materials to replace fossil fuels, but their production cost, especially for lipid extraction, still must be lowered substantially for field application. Although lipid extraction from concentrated wet microalgae using a nonpolar solvent is considered as a feasible method, an effective recovery method to regain the nonpolar solvent with microalgal lipid from the emulsified extraction mixture has not yet been addressed significantly. In this study, microalgal lipid is cost-efficiently recovered in continuous manner directly from the emulsified, highly concentrated extraction mixture by utilizing a surface-modified filter. The surface of a highly porous sponge filter is modified conformally by an oil-absorbing but water-repellent polymer coating via an initiated chemical vapor deposition (iCVD) process. Concentrated wet Schizochytrium sp. ABC101 microalgal cells are disrupted, and the microalgal lipid components are extracted out by adding n-hexane in the aqueous disrupted microalgae. The surface-modified filter is capable of selective permeation of the n-hexane phase with microalgal lipid while blocking the water-phase permeation simply by immersing the filter into the emulsified extraction mixture. The absorbed n-hexane phase is recovered in a continuous manner by pumping it out. The continuous filter-based recovery system shows a high recovery yield of 95% and an extremely high permeation flux of 2640 L m-2 h-1. Moreover, the recovery performance is maintained for more than 24 h without any filter-cleaning step. Techno-economic analysis of the method developed in this study with the conventional phase recovery methods shows that the rapid but highly cost-efficient filter-based recovery method will be a useful platform for scalable, continuous microalgae lipid production.

Anti-inflammatory effects of Lactobacillus reuteri LM1071 via MAP kinase pathway in IL-1ß-induced HT-29 cells.

Lactic acid bacteria are well-known probiotics, conferring several health benefits. In this study, we isolated lactobacilli from human breast milk and identified Lactobacillus reuteri LM1071 (RR-LM1071) using 16S rDNA sequencing. We tested the hemolytic activity, biogenic amine production, and antibiotic susceptibility of this strain to assess its safety. RR-LM1071 was found to be negative for hemolytic activity and biogenic amine production, as well as was measured in susceptible level for antibiotics in the minimal inhibitory concentration (MIC) test. The adhesive properties of RR-LM1071 were higher than those of LGG in HT-29 cells, and showed a greater hydrophobicity than LGG in hexadecane solvent. Under inflammatory conditions, RR-LM1071 suppressed the mRNA expression of IL-6, TNF-α, and IL-4 produced in IL-1ß-induced HT-29 cells. Our results suggest that RR-LM1071 is a safe and valuable probiotic that can be used for the treatment of inflammatory bowel disease.

Two-Dimensional Temperature Measurement in a High-Temperature and High-Pressure Combustor Using Computed Tomography Tunable Diode Laser Absorption Spectroscopy (CT-TDLAS) with a Wide-Scanning Laser at 1335-1375 nm.

Tunable diode laser absorption spectroscopy (TDLAS) technology is a developing method for temperature and species concentration measurements with the features of non-contact, high precision, high sensitivity, etc. The difficulty of two-dimensional (2D) temperature measurement in actual combustors has not yet been solved because of pressure broadening of absorption spectra, optical accessibility, etc. In this study, the combination of computed tomography (CT) and TDLAS with a wide scanning laser at 1335-1375 nm has been applied to a combustor for 2D temperature measurement in high temperature of 300-2000 K and high pressure of 0.1-2.5 MPa condition. An external cavity type laser diode with wide wavelength range scanning at 1335-1375 nm was used to evaluate the broadened H2O absorption spectra due to the high-temperature and high-pressure effect. The spectroscopic database in high temperature of 300-2000 K and high pressure of 0.1-5.0 MPa condition has been revised to improve the accuracy for temperature quantitative analysis. CT reconstruction accuracy was also evaluated in different cases, which presented the consistent temperature distribution between CT reconstruction and assumed distributions. The spatial and temporal distributions of temperature in the high-temperature and high-pressure combustor were measured successfully by CT-TDLAS using the revised spectroscopic database.

Hepatoprotective Effects of Streptococcus thermophilus LM1012 in Mice Exposed to Air Pollutants.

In this study, we explored whether the use of Streptococcus thermophilus LM1012 (TL-LM1012) as a safe probiotic exerts hepatoprotective effects by suppressing oxidative stress and inflammation in vitro and alleviating aspartate aminotransferase (AST), alanine aminotransferase (ALT), and lactate dehydrogenase (LDH) production in vivo. In a series of safety tests, TL-LM1012 was found to have a negative response to hemolysis and biogenic amines, as well as susceptibility to antibiotics. TL-LM1012 protected cell viability and suppressed cytotoxicity by inhibiting oxidative stress and induced heme oxygenase-1 and superoxide dismutase activity in a dose-dependent manner in diesel exhaust particulate matter (DEPM)-treated HepG2 cells. Moreover, proinflammatory cytokines, including tumor necrosis factor-α, interleukin (IL)-6, and IL-1ß, were suppressed in DEPM-treated splenocytes. In DEPM-treated mice, oral administration of TL-LM1012 regulated AST, ALT, and LDH production in the serum after 14 days of treatment. These findings indicate that TL-LM1012, a safe probiotic, provides a potent preventive or therapeutic effect against liver disease caused by air pollution.

Suppressive Effects of TSAHC in an Experimental Mouse Model and Fibroblast-Like Synoviocytes of Rheumatoid Arthritis.

The purpose of this study is to investigate the effect of TSAHC [4'-(p-toluenesulfonylamido)-4-hydroxychalcone] in K/BxN serum transfer arthritis model and fibroblast-like synoviocytes of rheumatoid arthritis (RA-FLS). In in vivo experiments, TSAHC attenuated the incidence and severity of arthritis in comparison with the vehicle group. Histological findings showed that TSAHC decreased the inflammation, bone erosion, cartilage damage, and osteoclasts activity in the ankle. Furthermore, we confirmed by biochemical analysis that the observations were associated with the decreased expression of proinflammatory cytokines, matrix metalloproteinases (MMPs), and RANKL in serum and ankle. In in vitro experiments, TSAHC induced apoptosis, while it significantly suppressed tumor necrosis factor-α (TNF-α)-induced cell proliferation in RA-FLS. Moreover, TSAHC inhibited mRNA expression of TNF-α-induced interleukin (IL)-6, MMP-1, MMP-3, and MMP-13. Evaluation of signaling events showed that TSAHC inhibited the translocation and transcriptional activity of nuclear factor-kappa B (NF-κB) by regulating phosphorylated-IκB-α (p-IκB-α) and IκB-α in TNF-α-induced RA-FLS. Our results suggest that TSAHC inhibits experimental arthritis in mice and suppresses TNF-α-induced RA-FLS activities via NF-κB pathway. Therefore, TSAHC may have therapeutic potential for the treatment of RA.

Myeloid deletion of SIRT1 suppresses collagen-induced arthritis in mice by modulating dendritic cell maturation.

The type III histone deacetylase silent information regulator 1 (SIRT1) is an enzyme that is critical for the modulation of immune and inflammatory responses. However, the data on its role in rheumatoid arthritis (RA) are limited and controversial. To better understand how SIRT1 regulates adaptive immune responses in RA, we evaluated collagen-induced arthritis (CIA) in myeloid cell-specific SIRT1 knockout (mSIRT1 KO) and wild-type (WT) mice. Arthritis severity was gauged on the basis of clinical, radiographic and pathologic scores. Compared with their WT counterparts, the mSIRT1 KO mice exhibited less severe arthritis, which was less destructive to the joints. The expression levels of inflammatory cytokines, matrix metalloproteinases and ROR-γT were also reduced in the mSIRT1 KO mice compared with the WT mice and were paralleled by reductions in the numbers of Th1 and Th17 cells and CD80- or CD86-positive dendritic cells (DCs). In addition, impaired DC maturation and decreases in the Th1/Th17 immune response were observed in the mSIRT1 KO mice. T-cell proliferation was also investigated in co-cultures with antigen-pulsed DCs. In the co-cultures, the DCs from the mSIRT1 KO mice showed decreases in T-cell proliferation and the Th1/Th17 immune response. In this study, myeloid cell-specific deletion of SIRT1 appeared to suppress CIA by modulating DC maturation. Thus, a careful investigation of DC-specific SIRT1 downregulation is needed to gauge the therapeutic utility of agents targeting SIRT1 in RA.

Endogenous conversion of n-6 to n-3 polyunsaturated fatty acids attenuates K/BxN serum-transfer arthritis in fat-1 mice.

It is suggested that n-3 polyunsaturated fatty acids (PUFAs) can be used in the preventive or therapeutic management of rheumatoid arthritis (RA); however, controversial results have been reported. Here, we examined the effects of a decrease in the n-6/n-3 PUFA ratio on RA using fat-1 transgenic mice. First, we tested whether fat-1 expression modulated signaling pathways in fibroblast-like synoviocytes (FLSs) stimulated with tumor necrosis factor α (TNF-α). TNF-α activated p38 mitogen-activated protein kinase and increased phosphorylation of the signal transducer and activator of transcription 3 in wild type (WT) FLSs but not in fat-1 FLSs. Arthritis was induced by injection of K/BxN serum. Based on clinical scores, ankle thickness and pathological severity, we showed that WT mice developed clinically overt arthritis, whereas fat-1 mice showed attenuated arthritis. Moreover, fat-1 mice exhibited down-regulated local and systemic levels of inflammatory cytokines. Lastly, bone marrow-derived macrophages (BMMs) of WT mice differentiated into tartrate-resistant acid phosphatase-positive multinucleated osteoclasts, whereas the osteoclastogenenic process was suppressed in BMMs of fat-1 mice. The endogenous conversion of n-6 to n-3 PUFAs via fat-1 plays a key role in attenuation of RA; therefore, dietary supplementation of n-3 PUFAs may have therapeutic potential for the management of RA.