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Applying the emerging molecular networking strategy, an uncommon cembranoid orthoester, sarcotortin A (1), featuring a 3/14/8/5‐fused scaffold, an unusual eunicellane‐type diterpenoid, sarcotorolide A (2), and two new biscembranoids, ximaolides M and N (7 and 8), along with nine known terpenoids 3–6 and 9–13 were isolated from the Hainan soft coral Sarcophyton tortuosum. The structure and absolute configuration of all new compounds were established by a combination of spectroscopic data, X‐ray diffraction analysis, and/or quantum chemical computational approaches. The plausible biogenetic relationship among these skeletally different terpenoids was proposed and discussed. In in vitro bioassay, new compound 7 exhibited a remarkable inhibitory activity against protein tyrosine phosphatases 1B (PTP1B) with the IC50 value of 8.06 μM. In addition, compounds 4 and 10 displayed significant inhibitory effects on lipopolysaccharide (LPS)‐induced inflammatory responses in RAW264.7 macrophages cells with the IC50 values of 19.13 and 16.45 μM, respectively. Compound 9 showed interesting cytotoxicity against H1975, MDA‐MB231, A549, and H1299 cancer cell lines with IC50 values of 31.59, 34.96, 43.87, and 27.93 μM, respectively. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A detailed chemical investigation of the South China Sea nudibranch Hexabranchus sanguineus, as well as its possible sponge‐prey Acanthella cavernosa, led to the isolation of fifteen new nitrogenous sesquiterpenoids, namely ximaocavernosins A−O, including seven cadinanes (1—7), seven spiroaxanes (12—18) and one aromadendrane (19), together with thirteen known related compounds (8—11 and 20—28). Compounds (±)‐1—9 (except for 4 and 6) were further separated by chiral‐phase HPLC to their corresponding unequal enantiomers, respectively. Their structures and absolute configurations were determined by a combination of extensive spectroscopic data analysis, quantum mechanical nuclear magnetic resonance (QM‐NMR) methods, Mosher's method, X‐ray diffraction analysis and/or time‐dependent density functional theory/electronic circular dichroism (TDDFT‐ECD) calculation. The commonly existed nitrogenous sesquiterpenoids in these two animals are suggested to be chemical markers for their prey‐predator relationship. [ABSTRACT FROM AUTHOR]

An amine-containing non-interpenetrating pillar-layer framework, [Zn2(dbtcb)( L1)] ⋅ x solvent ( 1), has been synthesized from Zn(NO3)2 and the ligands 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene (H4DBTCB) and 2,5-bis(4-pyridyl)aniline ( L1). The [Zn2(COO)4] secondary building units (SBUs) are bridged by DBTCB to form two-dimensional layers that are linked by L1 ligands acting as pillars to form a three-dimensional network. This NH2-containing framework can undergo versatile tailoring through post-synthetic covalent modification, solvent-assisted linker exchange (SALE), and single-crystal-to-single-crystal (SC-SC) transmetalation reactions. Acetamide-functionalized [Zn2( L2)(dbtcb)] ⋅ xsolvent ( 2) could be obtained by direct synthesis from Zn(NO3)2, N-acetyl-2,5-bis(4-pyridyl)aniline ( L2) and H4DBTCB. Importantly, compound 1 with pure NH2 ligands as pillars could be obtained by SALE of 2 with L1 in DMSO solution. The transmetalation reactions of 1 with CuII, NiII, and CoII were studied; inductively coupled plasma-atomic emission (ICP) analysis revealed that 1 underwent almost complete SC-SC transmetalation with CuII within 30 h, whereas with NiII and CoII only 70 and 80 % substitutions were achieved. Photoluminescence studies revealed that 1 and 2 display yellow-green and UV emission, respectively, under a UV lamp. Furthermore, the photoluminescent properties could be tuned by introducing mixed pillar amino ligands L1 and L2 into the MOF to produce multivariate (MTV) MOF 3 displaying overall orange emission. [ABSTRACT FROM AUTHOR]

The lysine 63 deubiquitinase cylindromatosis (CYLD) is expressed at high levels in the brain and is considered to be involved in anxious and depressive behavior, cognitive inflexibility, and autism disorders. Previous research was limited in some brain regions, including the hippocampus, striatum, and amygdala. To better understand whether CYLD plays a role in adaptation to stress and which brain regions are involved, we analyzed the behavior of CYLD-knockout mice in the elevated plus maze (EPM) and light-dark box test (LDT) after acute restraint stress (ARS) and mapped their c-Fos immunoreactivity in brain sections. Here we report that CYLD deficiency leads to an unexpected reaction to ARS in mice, and is accompanied by significant neuronal activation of brain regions including the medial prefrontal cortex (mPFC), dorsal striatum (DS), nucleus accumbens (NAc), and basal lateral amygdala (BLA), but not ventral hippocampus (vHPC). Our findings show that CYLD participates in ARS-induced anxious behavior and that this involves multiple brain regions.

Nanolobatone A, featuring an unprecedented tricyclo[10.3.0.0 1,2 ]pentadecane carbon skeleton, along with four new polyoxygenated and four unusual endoperoxide-bridged casbane-type diterpenoids were isolated from the Hainan soft coral Sinularia nanolobata. The structures of the new compounds were established by extensive spectroscopic analysis, X-ray diffraction analysis, and time-dependent density functional theory/electronic circular dichroism calculations. A plausible biosynthetic pathway of new isolates was proposed. Bioassays revealed that nanolobatone A showed weak antibacterial activity against the Gram-positive bacteria Streptococcus pyogenes., (© 2023 Wiley-VCH GmbH.)

Applying the emerging molecular networking strategy, an uncommon cembranoid orthoester, sarcotortin A (1), featuring a 3/14/8/5-fused scaffold, an unusual eunicellane-type diterpenoid, sarcotorolide A (2), and two new biscembranoids, ximaolides M and N (7 and 8), along with nine known terpenoids 3-6 and 9-13 were isolated from the Hainan soft coral Sarcophyton tortuosum. The structure and absolute configuration of all new compounds were established by a combination of spectroscopic data, X-ray diffraction analysis, and/or quantum chemical computational approaches. The plausible biogenetic relationship among these skeletally different terpenoids was proposed and discussed. In in vitro bioassay, new compound 7 exhibited a remarkable inhibitory activity against protein tyrosine phosphatases 1B (PTP1B) with the IC 50 value of 8.06 μM. In addition, compounds 4 and 10 displayed significant inhibitory effects on lipopolysaccharide (LPS)-induced inflammatory responses in RAW264.7 macrophages cells with the IC 50 values of 19.13 and 16.45 μM, respectively. Compound 9 showed interesting cytotoxicity against H1975, MDA-MB231, A549, and H1299 cancer cell lines with IC 50 values of 31.59, 34.96, 43.87, and 27.93 μM, respectively., (© 2022 Wiley-VCH GmbH.)

An amine-containing non-interpenetrating pillar-layer framework, [Zn 2 (dbtcb)(L1)]⋅x solvent (1), has been synthesized from Zn(NO 3 ) 2 and the ligands 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene (H 4 DBTCB) and 2,5-bis(4-pyridyl)aniline (L1). The [Zn 2 (COO) 4 ] secondary building units (SBUs) are bridged by DBTCB to form two-dimensional layers that are linked by L1 ligands acting as pillars to form a three-dimensional network. This NH 2 -containing framework can undergo versatile tailoring through post-synthetic covalent modification, solvent-assisted linker exchange (SALE), and single-crystal-to-single-crystal (SC-SC) transmetalation reactions. Acetamide-functionalized [Zn 2 (L2)(dbtcb)]⋅xsolvent (2) could be obtained by direct synthesis from Zn(NO 3 ) 2 , N-acetyl-2,5-bis(4-pyridyl)aniline (L2) and H 4 DBTCB. Importantly, compound 1 with pure NH 2 ligands as pillars could be obtained by SALE of 2 with L1 in DMSO solution. The transmetalation reactions of 1 with Cu II , Ni II , and Co II were studied; inductively coupled plasma-atomic emission (ICP) analysis revealed that 1 underwent almost complete SC-SC transmetalation with Cu II within 30 h, whereas with Ni II and Co II only 70 and 80 % substitutions were achieved. Photoluminescence studies revealed that 1 and 2 display yellow-green and UV emission, respectively, under a UV lamp. Furthermore, the photoluminescent properties could be tuned by introducing mixed pillar amino ligands L1 and L2 into the MOF to produce multivariate (MTV) MOF 3 displaying overall orange emission., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)