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Chemical structures of five coals from Mongolia were studied using solid-state C-13 NMR and oil and gas potential as well as yields of liquefaction products of the coals have been predicted. Pennsylvanian ZG, Upper Permian TT and Lower-Middle Jurassic AT-5 coals might have more potential for gas due to abundant aliphatic and aromatic CH3 carbons. Lower-Middle Jurassic KH coal probably has more potential for oil because of its increased CH2 content. Lower Cretaceous SO-3 coal may have more potential for gas, but significant amount of non-hydrocarbon gases could also be generated simultaneously. The prediction of yields of liquefaction product shows that ZG, TT and AT-5 and KH coals could yield similar hydrocarbon gas, oil and residue. Cretaceous SO-3 coal is predicted to give the lowest yields of oil, hydrocarbon gas and residue compared with others. KH sample has the highest oil yield due to its high content of CH2. Keywords: coal, petroleum potential, NMR, Mongolia

This work shows that hydroboration can be efficiently applied to the postsynthetic modification (PSM) of the Sonogashira-Hagihara coupling-based microporous organic polymers (MOPs). Hollow MOPs (H-MOPs) were prepared by template synthesis through the Sonogashira-Hagihara coupling of tetra(4-ethynylphenyl)methane with 1,4-diiodobenzene. The H-MOPs were used as platforms in the PSM-based functionalization. The heat-treatment of H-MOPs in the presence of a neat pinacolborane reagent resulted in the successful addition of pinacolborane groups to the internal alkynes of H-MOPs, generating H-MOPs with pinacolboranes (H-MOP-BPs). The pinacolborane moieties in the H-MOP-BP were further converted to boronic acid groups. The resultant H-MOP-BAs were used as heterogeneous organocatalysts in the CO

C18 trihydroxy fatty acids (THFAs), plant oxylipins, are used as antifungal agents and vaccine adjuvants.

We suggest that 1,3-diynes are main reaction sites in the thiol–yne click-based main chain post-synthetic modification of conjugated microporous polymers.

Various factors related to growing conditions can influence the nutritional quality of plants, including vegetable crops, especially the contents of health-promoting phytochemicals. In this study, the phytochemical contents of spinach (Spinacia oleracea) cultivated under greenhouse and open field conditions were comparatively analyzed using a metabolomic approach with Mass Profiler Professional (MPP) software. S. oleracea, which is one of the well-known leafy vegetables belonging to the family Chenopodiaceae, is cultivated worldwide. Although the nutritional value of spinach is high, the phytochemical contents of spinach cultivated under greenhouse and open field conditions have not been comparatively analyzed. Metabolomic analysis of the methanol (MeOH) extracts of greenhouse-cultivated spinach (GS) and open field-cultivated spinach (OFS) using ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS), followed by principal component analysis (PCA) with MPP demonstrated the differential metabolite profiles of GS and OFS. The active compounds 1-3 were isolated and identified using LC-Q-TOF-MS-guided fractionation. Among these, 5,3',4'-trihydroxy-3-methoxy-6,7-methylenedioxyflavone 4'-glucuronide (2) exhibited growth-inhibitory activities against Helicobacter pylori 51. Distribution analysis of compound 2 revealed that the anti-H. pylori compound 2 is an OFS-specific bioactive phytochemical. This indicates that the phytochemical quality of OFS is better than that of GS. These findings will aid in providing vital data for vegetable processors, dieticians, nutritionists, and consumers to select optimal green leafy vegetables.

(-)-α-Bisabolol is a functional ingredient in various health and cosmetic products and has antibacterial, anti-inflammatory, and wound healing properties. (-)-α-Bisabolol is chemically synthesized and produced by steam distillation of essential oils extracted from Brazilian Candeia (Eremanthus erythropappus). To sustainably produce pure (-)-α-bisabolol, we previously engineered Escherichia coli to produce 9.1 g/L (-)-α-bisabolol via heterologous mevalonate pathways and (-)-α-bisabolol synthase (BOS) from German chamomile, Matricaria recutita (MrBOS). BOS has only been reported in MrBOS and Brazilian Candeia (EeBOS). The limited availability of BOS has made it difficult to achieve high titer and yield and large-scale (-)-α-bisabolol production. We identified a novel BOS in globe artichoke (CcBOS) and examined its functionality in vitro and in vivo. CcBOS showed higher catalytic efficiency and (-)-α-bisabolol production rates than those from MrBOS or EeBOS. In fed-batch fermentation, CcBOS generated the highest reported (-)-α-bisabolol titer to date (23.4 g/L). These results may facilitate economically viable industrial (-)-α-bisabolol production.

Telomeric repeat binding factor a (Terfa) derived from zebrafish is a homologous protein with human telomeric repeat binding factor 2 (TRF2). Terfa is known as a senescence-associated biomarker in various research through the zebrafish animal model. In addition, according to the findings so far, it has been confirmed that human or plant telomere binding proteins bind to telomeric DNA specialized for each species, but, in our result, Terfa shows it strongly binds to both human or plant type telomeric DNA. Here we characterized the DNA binding properties and demonstrate the solution structure of Terfa and identified residues participating in the interaction with both human and plant telomeric DNA. In DNA recognition of human and plant telomere binding proteins, the N-terminal loop and the α-helix 3 part of Myb domain were bound majorly, whereas, in the case of Terfa, the N-terminal loop, the α-helix 1-2 loop, and α-helix 2 of the Myb domain were dominantly bound. Therefore, when Terfa recognizes DNA, it was found that the binding module differs from previously known telomere binding proteins. The comparison of the structure of the telomere binding proteins provides an opportunity to understand more specifically how the structural properties of each telomere binding protein are associated with telomeric DNA binding from an evolutionary point of view.

Rechargeable calcium batteries have attracted increasing attention as promising multivalent ion battery systems due to the high abundance of calcium. However, the development has been hampered by the lack of suitable cathodes to accommodate the large and divalent Ca2+ ions at a high redox potential with sufficiently fast ionic conduction. Herein, we report a new intercalation host which presents 500 cycles with a capacity retention of 90% and a remarkable power capability at ~3.2 V (vs. Ca/Ca2+) in a calcium battery. The cathode material derived from Na0.5VPO4.8F0.7 is demonstrated to reversibly accommodate a large amount of Ca2+ ions, forming a series of CaxNa0.5VPO4.8F0.7 (0, Rechargeable calcium batteries are promising multivalent battery systems but the lack of suitable electrodes hampers their development. Here the authors report a cathode derived from polyanion framework that demonstrates uncommonly stable and fast intercalation behaviours of calcium ions.

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The reactor fouling is a notorious obstacle in managing continuous synthetic processes of polyketones. The fouling raises synthetic costs and reduces the bulk density of polymers. Thus, efficient seed materials are required for antifouling performance. Hollow microporous organic polymers (HMOPs) were prepared using ZIF-8 nanoparticles as templating materials. Sulfonic groups were incorporated into HMOP via a post synthetic approach. The resultant HMOP–SO3H (20–90 μg/mL in methanol) showed successful catalyst activation and antifouling performance in polyketone synthesis.

This work shows that the hydrogen evolution performance of conjugated microporous polymer (CMP)-based photocatalysts can be enhanced through their hollow shape engineering. Using a hollow microporous organic polymer (H-MOP) as a template, hollow Stille coupling-based CMP photocatalysts with Pd nanoparticles (H-MOP@SCMP-Pds) were prepared, showing enhanced hydrogen evolution rates up to 7100 μmol h−1 g−1 and apparent quantum yields up to 3.72% (@420 nm).

Conjugated microporous polymers (CMPs) have significant potential as electrode materials for electric energy storage devices due to their high surface areas, conjugation features, and chemical stability. However, low conductivity has limited their electrochemical performance. To realize the maximum capability of CMPs, a synthetic strategy for enhancing their conductivity is required. This work shows that during the synthesis of CMPs, carbon black (CB) nanoparticles can be entrapped in situ. Moreover, redox-active benzoquinone (BQ) species could be generated at the CMP to form CMP-BQ through post-synthetic modification. The resultant CB@CMP-BQs with the entrapped CB nanoparticles showed enhanced electrochemical performance as electrode materials for pseudocapacitors, compared with CMP-BQ. They showed capacitances up to 424 and 373 F g−1 at current densities of 0.5 and 1 A g−1, respectively. In addition, the optimal CB@CMP-BQ3 showed excellent cycling performance for 10 000 cycles.

This work introduces, for the first time, the energy harvesting performance of conjugated microporous polymers (CMPs) as tribo-positive materials for triboelectric nanogenerators (TENGs). Various nano or submicron CMP particles (CMP-X) were prepared by the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodoarenes. Optimized CMP-X nanoparticles in a polyurethane (PU) matrix showed excellent triboelectrification performance, displaying peak-to-peak voltages of up to 411 V and a maximum power density of 0.80 mW cm−2. Moreover, an optimized 5.0% CMP-H@PU-based TENG could be utilized as a power source for the charging of an electrolytic capacitor and for the operation of 100 LEDs.

Microporous organic polymer nanoparticles bearing tetraphenylethylene moieties (MOPTs) were prepared in the presence of poly(vinylpyrrolidone) (PVP). The PVP was entrapped into the microporous network of MOPT to form MOPT-P and played the roles of size control, porosity enhancement, and surface property management. MOPT materials without PVP showed superhydrophobicity with a water contact angle of 151°. In comparison, the MOPT-P showed excellent water compatibility. Moreover, due to the aggregation-induced emission property of tetraphenylethylene moieties, the MOPT-P showed emission and excellent emission-based sensing of nitrophenols in water with Ksv values in the range of 1.26 × 104 ∼ 3.37 × 104 M–1. It is noteworthy that the MOPT-P used water only as a sensing medium and did not require additional organic solvents to enhance water dispersibility of materials. The MOPT-P could be recovered and reused for the sensing at least five times.

Specialized proresolving mediators (SPMs), such as resolvins and maresins, resolve inflammation and protect against infection at trace amounts generated by neutrophils and macrophages in humans. Th...

Conjugated microporous polymer (CMP)-based energy-storage materials were developed for pseudocapacitors. Nanoparticulate CMP (N-CMP) with an average diameter of 41±4 nm was prepared through kinetic growth control in the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodobenzene. The N-CMP is rich in a diphenylacetylene moiety in its chemical structure. Through the FeCl3 -catalyzed oxidation of diphenylacetylene moieties, N-CMP with benzil moieties (N-CMP-BZ) was prepared and showed enhanced electrochemical performance as an electrode material of pseudocapacitors, compared with CMP, CMP-BZ, and N-CMP. In model studies, the benzil was redox active and showed two-electron reduction behavior. The excellent electrochemical performance of N-CMP-BZ is attributable to the enhanced utilization of functional sites by a nanosize effect and the additional redox contribution of benzil moieties.

This work introduces a so called “caffeine method” for morphology evolution of microporous organic polymer (MOP). In a proper reaction medium such as triethylamine, caffeine undergoes dynamic self-...

Multifunctional drug delivery systems were designed and engineered by template synthesis of a microporous organic polymer (MOP) and by postsynthetic modification. Hollow MOP spheres bearing Fe3O4 yolks (Fe3O4@Void@MOP) were prepared by the synthesis of MOP on Fe3O4@SiO2 nanoparticles and by successive silica etching. In addition to the magneto-thermal function of Fe3O4 yolks, an aggregation-induced emission (AIE) feature was incorporated into the Fe3O4@Void@MOP through a homocoupling of tetra(4-ethynylphenyl)ethylene to form Fe3O4@Void@MOP-TE. Folate groups were further introduced into Fe3O4@Void@MOP-TE through the postsynthetic modification based on the thiol-yne click reaction. The resultant Fe3O4@Void@MOP-TE-FA showed multifunctionality in antitumoral therapy via folate receptor targeting, doxorubicin delivery, AIE-based imaging, and the magneto-thermal feature.

Flexible and metal-economical electromagnetic interference (EMI) shielding films were fabricated based on microporous organic polymer (MOP) chemistry. MOP with amino groups (MOP-A) could be introduced to the surface of poly(ethylene terephthalate) (PET) fibers. Due to the microporosity and amino groups of MOP-A, Ag+ could be easily incorporated into PET@MOP-A. Through Ag-catalyzed electroless Cu deposition, PET@MOP-A@Cu films were fabricated. The morphological and chemical structures of the PET@MOP-A@Cu were characterized by scanning electron microscopy, X-ray diffraction studies, and X-ray photoelectron spectroscopy. Among the films, the PET@MOP-A@Cu-40 with 41 wt % Cu (a thickness of 0.64 μm) showed excellent EMI shielding performance with 64.3-73.8 dB against an EM of 8-12 GHz. Moreover, it showed retention of the original EMI shielding performance against 1000 bending (R = 5 mm) tests.

AMP-activated protein kinase (AMPK in human and AAK in C. elegans) is a master regulator of metabolism. It has many isotypes, but its isotype-dependent functions are largely unknown. By developing ...

Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form Stille coupling-based MOP (St-MOP)@Pd. The size of St-MOP particles and the amount of metallic Pd in St-MOP@Pd depended on the amount of Pd catalyst. As the amount of Pd catalyst increased, the size of St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and St-MOP@Pd showed excellent catalytic performance in the visible light-driven Suzuki–Miyaura coupling. The optimal St-MOP@Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h−1 in the visible light-driven Suzuki–Miyaura coupling of 1-acetyl-4-bromobenzene and phenylboronic acid at 25 °C. The optimal amount of St-MOP and metallic Pd in St-MOP@Pd was critical to achieve excellent catalytic performance. The overall photocatalytic principles of St-MOP@Pd were rationalized by computational simulation.

This work shows a new post-synthetic strategy of a microporous organic polymer (MOP) based on AB2 polymerization chemistry (polymerization of AB2-type monomers). Hollow MOP (H-MOP) platforms were prepared by template synthesis via Sonogashira coupling of 1,4-dibromo-2,5-diethynylbenzene. The amount of terminal alkynes in the H-MOP was amplified via AB2 polymerization. Through the thiol–yne click reaction, aliphatic sulfonic acids were incorporated into the terminal alkyne-enriched H-MOP. The resultant solid acid catalysts showed efficient performance in the synthesis of soluble cellulose derivatives.

This work shows that a hollow and microporous metal-free N,N'-phenylenebis(salicylideneimine) (salphen) network (H-MSN) can be engineered by Sonogashira coupling of [tetraiodo{di(Zn-salphen)}] building blocks with 1,4-diethynylbenzene in the presence of silica templates and by successive Zn and silica etching. Iron(III) ions could be incorporated into the H-MSN to form hollow and microporous Fe-disalphen networks (H-MFeSN) with enhanced microporosity and surface area. The H-MFeSN showed efficient catalytic performance and recyclability in the CO2 conversion to cyclic carbonates.

Phenalenone derivatives sourced from fungi are polyketides that have attracted significant interest because of their diverse chemical structures and potential bioactivities. As part of our ongoing quest to discover novel natural products with biological properties from diverse natural resources, three unreported phenalenone derivatives (1-3), named ent-12-methoxyisoherqueinone (1), (-)-scleroamide (2), and (+)-scleroamide (3), together with four known phenalenone derivatives, ent-atrovenetinone (4), isoherqueinone (5), herqueinone (6), and ent-peniciherquinone (7) were isolated from the Hawaiian soil fungus Penicillium herquei FT729, collected on the Big Island, Hawaii. Compounds 2 and 3 were enantiomers, which were separated using a chiral-phase HPLC column, which provided optically pure compounds 2 and 3. The structures of the novel compounds were established by extensive spectroscopic analyses, including 1D and 2D NMR and high-resolution ESIMS. Their absolute configurations were determined using quantum chemical electronic circular dichroism (ECD) calculations. The inhibitory activity of the isolated compounds (1-7) against indoleamine 2,3-dioxygenase 1 (IDO1) was assessed. Compounds 1, 5-7 inhibited IDO1, with IC

As part of ongoing systematic research into the discovery of bioactive secondary metabolites with novel structures from Korean wild mushrooms, we investigated secondary metabolites from a poisonous mushroom

Embedding metal-halide perovskite particles within an insulating host matrix has proven to be an effective strategy for revealing the outstanding luminescence properties of perovskites as an emerging class of light emitters. Particularly, unexpected bright green emission observed in a nominally pure zero-dimensional cesium–lead–bromide perovskite (Cs4PbBr6) has triggered intensive research in better understanding the serendipitous incorporation of emissive guest species within the Cs4PbBr6 host. However, a limited controllability over such heterostructural configurations in conventional solution-based synthesis methods has limited the degree of freedom in designing synthesis routes for accessing different structural and compositional configurations of these host–guest species. In this study, we provide means of enhancing the luminescence properties in the nominal Cs4PbBr6 powder through a guided heterostructural configuration engineering enabled by solid-state mechanochemical synthesis. Realized by an in-depth study on time-dependent evaluation of optical and structural properties during the synthesis of Cs4PbBr6, our target-designed synthesis protocol to promote the endotaxial formation of Cs4PbBr6/CsPbBr3 heterostructures provides key insights for understanding and designing kinetics-guided syntheses of highly luminescent perovskite emitters for light-emitting applications.

(-)-α-Bisabolol is a functional ingredient in various health and cosmetic products and has antibacterial, anti-inflammatory, and wound healing properties. (-)-α-Bisabolol is chemically synthesized and produced by steam distillation of essential oils extracted from Brazilian Candeia (

Lipoxygenases (LOXs) biosynthesize lipid mediators (LMs) as human signaling molecules. Among LMs, specialized pro-resolving mediators (SPMs) are involved in the resolution of inflammation and infection in humans. Here, the putative LOX from the bacterium Sphingopyxis macrogoltabida was identified as arachidonate 9S-LOX. The enzyme catalyzed oxygenation at the n-12 position of C20 and C22 polyunsaturated fatty acids (PUFAs) to form 9S- and 11S-hydroperoxy fatty acids, which were reduced to 9S- and 11S-hydroxy fatty acids (HFAs) by cysteine, respectively, and it catalyzed again oxygenation at the n-6 position of HFAs to form 9S,15S- and 11S,17S-DiHFAs, respectively. The regioselective residues of 9S-LOX were determined as lle395 and Val569 based on the amino acid alignment and homology models. The regioselectivity of the I395F variant was changed from the n-12 position on C20 PUFA to the n-6 position to form 15S-HFAs. This may be due to the reduction of the substrate-binding pocket by replacing the smaller Ile with a larger Phe. The V569W variant had a significantly lower second‑oxygenating activity compared to wild-type 9S-LOX because the insertion of the hydroxyl group of the first‑oxygenating products at the active site was seemed to be hindered by substituting a larger Trp for a smaller Val. The compounds, 11S-hydroxydocosapentaenoic acid, 9S,15S-dihydroxyeicosatetraenoic acid, 9S,15S-dihydroxyeicosapentaenoic acid, 11S,17S-hydroxydocosapentaenoic acid, and 11S,17S-dihydroxydocosahexaenoic acid, were newly identified by polarimeter, LC-MS/MS, and NMR. 11S,17S-DiHFAs as SPM isomers biosynthesized from C22 PUFAs showed anti-inflammatory activities in mouse and human cells. Our study contributes may stimulate physiological studies by providing new LMs.