Acyl-CoA dehydrogenase long chain (ACADL) is a target protein of stylissatin A, an anti-inflammatory cyclic heptapeptide.

Stylissatin A (SA) is a cyclic heptapeptide isolated from the marine sponge Stylissa massa. SA shows anti-inflammatory activity against lipopolysaccharide (LPS)-stimulated murine RAW264.7 macrophage cells, but the detailed mechanism of action remains unclear.

Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy.

We introduce a novel NMR approach that extends the capabilities of indirect dynamic nuclear polarization (DNP) under magic-angle spinning to probe the local environment of half-integer spin quadrupolar nuclei. Compared to cross-polarization, this novel method based on the refocused INEPT scheme with adiabatic dipolar recoupling is easier to optimize and does not distort the quadrupolar line shapes. Furthermore, the use of this technique, instead of the PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order) scheme or direct DNP, greatly improves the sensitivity of DNP-NMR for the detection of quadrupolar isotopes with small dipolar couplings to protons, including notably those located in the subsurface of inorganic materials or with low gyromagnetic ratio (γ).

Cascade Reaction-Based Chemiresistive Array for Ethylene Sensing.

Chemiresistive sensors, which are based on semiconducting materials, offer real-time monitoring of environment. However, detection of nonpolar chemical substances is often challenging because of the weakness of the doping effect. Herein, we report a concept of combining a cascade reaction (CR) and a chemiresistive sensor array for sensitive and selective detection of a target analyte (herein, ethylene in air).

Synthesis of 2-(2-Hydroxyethoxy)-3-hydroxysqualene and Characterization of Its Anti-Inflammatory Effects.

Squalene (SQ), a natural precursor of many steroids, can inhibit tumor progression and decrease serum cholesterol levels. However, it is difficult to discern the effect of highly active molecules in the treatment of diseases because not enough active compounds reach the site of pathology in crowded biosystems. Therefore, it is necessary to design artificial probes that work effectively within crowded systems.

Facile Construction of Furanoacenes by a Three-Step Sequence Going through Disilyl-exo-cyclic Dienes.

Facile synthesis of various benzonaphthofurans was achieved by intramolecular hydroarylation of 1,4-disilyl-2-aryloxy-1,3-enynes followed by cycloaddition with arynes or alkenes and finally desilylaromatization. The three-step transformation can be operated sequentially in one-pot, providing with a range of furanoacenes easily and highly effectively.

DNP NMR spectroscopy of cross-linked organic polymers: rational guidelines towards optimal sample preparation.

Cross-linked polystyrenes (PS) are an important class of polymers, whose properties are strongly dependent on incorporated functionalities, for which detailed understanding of their structure remains a challenge. Here, we develop a rational guideline for dynamic nuclear polarization (DNP) sample formulation for cross-linked PS to interrogate their structure. We show that the DNP enhancement on a series of cross-linked PS bearing alkylammonium groups as prototypical organic polymers correlates with the polymer swelling properties in both apolar and polar formulations (TEKPol/1,1,2,2-tetrachloroethane and AMUPol/dimethyl sulfoxide).

Efficient Photocatalytic CO Reduction by a Ni(II) Complex Having Pyridine Pendants through Capturing a Mg Ion as a Lewis-Acid Cocatalyst.

We have synthesized a new Ni(II) complex having an SN-tetradentate ligand with two noncoordinating pyridine pendants as binding sites of Lewis-acidic metal ions in the vicinity of the Ni center, aiming at efficient CO production in photocatalytic CO reduction. In the presence of Mg ions, enhancement of selective CO formation was observed in photocatalytic CO reduction by the Ni complex with the pyridine pendants through the formation of a Mg-bound species, as compared to the previously reported Ni complex without the Lewis-acid capturing sites. A higher quantum yield of CO evolution for the Mg-bound Ni complex was determined to be 11.

Isorhamnetin Alleviates Steatosis and Fibrosis in Mice with Nonalcoholic Steatohepatitis.

Nonalcoholic steatohepatitis (NASH) is the most severe and progressive form of nonalcoholic fatty liver disease (NAFLD), which can lead to life-threatening conditions, however, there is still no approved drug for the treatment of NASH. In this study we used human-like NASH mouse model and treated orally with isorhamnetin at a dose of 50 mg/kg to analyze the effect of isorhamnetin on the progression of NASH. NASH-induced mice represented severe steatosis with inflammation, and fibrosis in liver accompanied with high level of liver injury markers in serum.

Antifibrotic effect of methylated quercetin derivatives on TGFβ-induced hepatic stellate cells.

Quercetin (QCT) and isorhamnetin (ISO), natural flavonoids, were both shown to possess antifibrotic activity in and models of hepatic fibrosis. Although ISO is a direct metabolite of QCT differing by a methyl group, it has been reported to be absorbed more adequately and eliminated slower than QCT after oral administration. Our aim of the study was to investigate biological effect of mono-methylated QCT derivatives against fibrosis using rat hepatic stellate cells (HSC-T6).

Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear Ru-Co Complex with Adjacent Reaction Sites.

We have designed and synthesized a hetero-dinuclear Ru-Co complex with a dinucleating ligand inspired by hetero-dinuclear active sites of metalloenzymes. A synergistic effect between the adjacent Ru and Co sites has been confirmed in catalytic olefin hydrogenation by the complex, exhibiting a much higher turnover number than those of mononuclear Ru or Co complexes as the components. A Ru-hydrido species was detected by H NMR and electrospray ionization (ESI)-time-of-flight (TOF)-MS measurements as an intermediate to react with olefins, and Co-bound methanol was suggested to act as a proton source.

Antidepressant-Like Effect of Ferulic Acid via Promotion of Energy Metabolism Activity.

Scope: Ferulic acid (FA), a natural phenolic phytochemical abundantly present in whole grains, herbs, and dried fruits, exhibits anti-inflammatory, antioxidant, and neuroprotective effects. In the present study, the antidepressant-like effects of FA in male ICR mice using tail suspension test (TST) are investigated and its molecular mechanisms are explored.

Methods And Results: Oral administration of FA at a dose of 5 mg kg for 7 days significantly reduces immobility of mice compared to vehicle-administered control group.

Elucidation of the Molecular Mechanism Underlying (Lim.)-Induced Relaxation and Anti-Depression.

ethanolic extract (VEE) and verbascoside (Vs), a phenypropanoid glycoside, have been demonstrated to exert relaxant and anxiolytic properties. However, the molecular mechanisms behind their effects are still unclear. In this work, we studied the effects and action mechanisms of VEE and Vs and , on human neurotypic SH-SY5Y cells.

Metal-Oxyl Species and Their Possible Roles in Chemical Oxidations.

Metal-oxyl (M-O) complexes having an oxyl radical ligand, which are electronically equivalent to well-known metal-oxo (M═O) complexes, are surveyed as a new category of metal-based oxidants. Detection and characterization of M-O species have been made in some cases, although proposals and characterization of the species are mostly done on the basis of density functional theory (DFT) calculations. The reactivity of M-O complexes will provide a way to achieve potentially difficult oxidative conversion of substrates.

Titania-Catalyzed HO Thermal Oxidation of Styrenes to Aldehydes.

We investigated the selective oxidation of styrenes to benzaldehydes by using a non-irradiated TiO-HO catalytic system. The oxidation promotes multi-step reactions from styrenes, including the cleavage of a C=C double bond and the addition of an oxygen atom selectively and stepwise to provide the corresponding benzaldehydes in good yields (up to 72%). These reaction processes were spectroscopically shown by fluorescent measurements under the presence of competitive scavengers.

Modulation of the neurotransmitter systems through the anti-inflammatory and antidepressant-like effects of squalene from Aurantiochytrium sp.

Although algae have been the focal point of biofuel research, studies on their biological activities have been limited. In recent years, however, the importance of algae as sources of functional ingredients has been recognized due to their health beneficial effects. In this study, we evaluated the antidepressant-like activities of ethanol extract of Aurantiochytrium sp.

Structural exploration of rhodium catalysts and their kinetic studies for efficient parahydrogen-induced polarization by side arm hydrogenation.

Parahydrogen-induced polarization (PHIP) is a rapid and cost-effective hyperpolarization technique using transition metal-catalysed hydrogenation with parahydrogen. We examined rhodium catalysts and their kinetic studies, rarely considered in the research of current PHIP. It emerged that rhodium complexes with electron-donating bisphosphine ligands, with a dicyclohexylphosphino group, appear to be more effective than conventional rhodium catalysts.

Synthesis of hydrosilanes via Lewis-base-catalysed reduction of alkoxy silanes with NaBH.

Hydrosilanes were synthesized by reduction of alkoxy silanes with BH in the presence of hexamethylphosphoric triamide (HMPA) as a Lewis-base catalyst. The reaction was also achieved using an inexpensive and easily handled hydride source NaBH, which reacted with EtBr as a sacrificial reagent to form BHin situ.

Heterogeneous hydrosilylation reaction catalysed by platinum complexes immobilized on bipyridine-periodic mesoporous organosilicas.

The utility of a bipyridine periodic mesoporous organosilica, BPy-PMO, as a support material of a hydrosilylation catalyst was investigated in the hydrosilylation of phenylacetylene with trimethoxysilane. [PtMe2(BPy-PMO)] (1) exhibited a moderate catalytic activity, whereas the reaction was successfully catalysed by [PtMe2(BPy-PMO-TMS)] (2) bearing end-capped TMS groups on the surface. Spectroscopic analyses of 2 revealed that the porous structure of BPy-PMO-TMS remained almost unchanged through the reaction.

3,4,5-Tricaffeoylquinic acid induces adult neurogenesis and improves deficit of learning and memory in aging model senescence-accelerated prone 8 mice.

Caffeoylquinic acid (CQA) is a natural polyphenol with evidence of antioxidant and neuroprotective effects and prevention of deficits in spatial learning and memory. We studied the cognitive-enhancing effect of 3,4,5-tricaffeoylquinic acid (TCQA) and explored its cellular and molecular mechanism in the senescence-accelerated mouse prone 8 (SAMP8) model of aging and Alzheimer's disease as well as in human neural stem cells (hNSCs). Mice were fed with 5 mg/kg of TCQA for 30 days and were tested in the Morris water maze (MWM).

On the Geometrical Stability of Square-Planar Platinum(0) Complexes That Bear a PNP-Pincer-Type Phosphaalkene Ligand (Eind -BPEP).

The four-coordinate Pt complex [Pt(PPh )(Eind -BPEP)] (Eind=1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl; BPEP=2,6-bis(1-phenyl-2-phosphaethenyl)pyridine), which bears a PNP-pincer-type phosphaalkene ligand (Eind -BPEP; PNP=N,N-bis(diphenylphosphine)-2,6-diaminopyridine), were found to adopt a square-planar configuration around the Pt center (τ =0.11). This coordination geometry is very uncommon for formal d complexes.

Exploiting Intermolecular Interactions between Alkyl-Functionalized Redox-Active Molecule Pairs to Enhance Interfacial Electron Transfer.

The strategies to enhance electron transfer rates between redox-active, light-harvesting molecules attached to semiconductor surfaces and redox mediators in solution by modifying molecular structure are not fully investigated yet. Therefore, the design of molecules with controlled electron transfer rates remains a challenge. The aims of this work are to quantify the effect of long alkyl chain substitution on the electron transfer from cobalt(II/III) tris(2,2'-bipyridine) to organic molecules containing carbazole and thiophene and to demonstrate that alkyl chains can be used to enhance electron transfer between donor-acceptor pairs.

Observation of proximities between spin-1/2 and quadrupolar nuclei in solids: Improved robustness to chemical shielding using adiabatic symmetry-based recoupling.

We introduce a novel heteronuclear dipolar recoupling based on the R2 symmetry, which uses the tanh/tan (tt) shaped pulse as a basic inversion element and is denoted R2(tt). Using first-order average Hamiltonian theory, we show that this sequence is non-γ-encoded and that it reintroduces the |m| = 1 spatial component of the Chemical Shift Anisotropy (CSA) of the irradiated isotope and its heteronuclear dipolar interactions. Using numerical simulations and one-dimensional (1D) Al-{P} through-space D-HMQC (Dipolar Heteronuclear Multiple-Quantum Correlation) experiments on VPI-5, we compare the performances of this recoupling to those of other non-γ-encoded |m| = 1 heteronuclear recoupling schemes: REDOR (Rotational-Echo DOuble Resonance), SFAM (Simultaneous Frequency and Amplitude Modulation) and R4(tt).

Sequence-Controlled Catalytic One-Pot Synthesis of Siloxane Oligomers.

Silicones are highly valuable poly- and oligomeric materials with a broad range of applications due to their outstanding physicochemical properties. The core framework of silicone materials consists of siloxane (Si-O-Si) bonds, and thus, the development of efficient siloxane-bond-forming reactions has attracted much attention. However, these reactions, especially "catalytic" siloxane-bond-forming reactions that enable the selective formation of unsymmetrical siloxane bonds, remain relatively underdeveloped.

Mechanistic Insights into Homogeneous Electrocatalytic and Photocatalytic Hydrogen Evolution Catalyzed by High-Spin Ni(II) Complexes with SN-Type Tetradentate Ligands.

We report homogeneous electrocatalytic and photocatalytic H evolution using two Ni(II) complexes with SN-type tetradentate ligands bearing two different sizes of chelate rings as catalysts. A Ni(II) complex with a five-membered SCS-Ni chelate ring (1) exhibited higher activity than that with a six-membered SCS-Ni chelate ring (2) in both electrocatalytic and photocatalytic H evolution despite both complexes showing the same reduction potentials. A stepwise reduction of the Ni center from Ni(II) to Ni(0) was observed in the electrochemical measurements; the first reduction is a pure electron transfer reaction to form a Ni(I) complex as confirmed by electron spin resonance measurements, and the second is a 1e/1H proton-coupled electron transfer reaction to afford a putative Ni(II)-hydrido (Ni-H) species.