Correction: Nukulkit et al. Eight Indole Alkaloids from the Roots of Maerua siamensis and Their Nitric Oxide Inhibitory Effects. Molecules 2022, 27, 7558.

After a proofreading check, some experimental data were inconsistent with the supplementary information in the original publication [...].

A new benzoquinone and a new stilbenoid from Paphiopedilum exul (Ridl.) Rolfe.

One new alkyl benzoquinone, paphionone (1), one new trans-stilbenoid, (E)-6,5'-dihydroxy-2,3'-dimethoxystilbene (2), and eight known stilbenoids and flavonoids (3-10) were isolated from the leaves and roots of Paphiopedilum exul (Orchidaceae). Their chemical structures were determined based on IR, ECD, MS and NMR analyses. Cytotoxicity of all isolated compounds towards human hepatocellular carcinoma (HepG2) cell line was examined in vitro by MTT assay. The para-hydroxybenzyl substituted stilbene 10 was potently cytotoxic to the cancer cells, with an IC50 value of 4.80 ± 1.10 µM (selectivity index = 20.83). All compounds were non-toxic to normal human embryo fibroblast (OUMS-36) cell line.

Insights into Selective Mechanism of NiO-TiO2 Heterojunction to H2 and CO.

The construction of p-n heterojunctions has become a widely adopted strategy for achieving the selective detection of reducing gases, including H2 and CO. Nevertheless, the elucidation of the gas selectivity mechanism at the nanoscale remains elusive. First-principle calculations provide an attractive avenue for comprehending the influence of coordination structures on gas-sensitive selectivity, thereby unveiling the structure-activity relationship of p-n heterojunction sites. In this study, we investigate the selective adsorption behavior of H2 and CO on a NiO-TiO2 heterojunction using density functional theory. The results of d-band center analysis confirm that the NiO-TiO2 heterojunction with adsorbed oxygen significantly enhances the adsorption stability of reducing gases. Intriguingly, our calculations reveal that H2 has a higher affinity for adsorbed oxygen on the heterojunction surface compared to that of CO, corresponding to a lower H2 adsorption energy. Density of states (DOS) results indicate that the NiO-TiO2 heterojunction, with preadsorbed oxygen, exhibits ultrahigh selectivity with an n-type gas-sensitive response to H2, effectively eliminating the cross-sensitivity observed with CO, as confirmed by gas-sensitive characterization research. The sensing mechanism of the NiO-TiO2 heterojunction's selective detection of H2 without interference from CO can be visually explained by electron transfer and potential barrier changes, paving the way for future developments in novel, selective gas-sensitive materials.

Schomburginones A‒J, geranylated benzophenones from the leaves of Garcinia schomburgkiana and their cytotoxic and anti-inflammatory activities.

Ten undescribed benzophenones, schomburginones A-J, together with 14 known analogs were isolated from the leaves of Garcinia schomburgkiana, an edible plant native to the Indochina region. The structures of the undescribed compounds were elucidated by NMR combined with HRMS spectroscopy, while their absolute configurations were determined using ECD and single-crystal X-ray diffraction analysis. The isolated metabolites represent benzophenone derivatives containing a modified monoterpene unit, including tri- and tetracyclic skeletons, which are rarely found in genus Garcinia. The cytotoxic evaluation on three cancerous cell lines demonstrated that schomburginone G, schomburginone H, and 3-geranyl-2,4,6-trihydroxybenzophenone were active against HeLa cells with IC50 values in the range of 12.2-15.7 µM, respectively, and selective compared to the non-cancerous L929 cells (SI > 3.5). In addition, the three cytotoxic compounds together with clusiacyclol A showed significant NO inhibitory activity in RAW 264.7 macrophage cells over 85% inhibition without obvious cytotoxicity at a final concentration of 100 µM. The promising activities of these compounds in cytotoxic and anti-inflammatory assays make them attractive for further study in the development of anticancer drugs.

Immunomodulatory Effects of New Phenanthrene Derivatives from Dendrobium crumenatum.

Three new phenanthrene derivatives (1, 2, 4), one new fluorenone (3), and four known compounds (5-8) were isolated from the ethyl acetate extract of Dendrobium crumenatum Sw. stems using column chromatography. The chemical structures were elucidated by analysis of spectroscopic data. The absolute configuration of 4 was determined by electronic circular dichroism calculation. We also evaluated the immunomodulatory effects of compounds isolated from D. crumenatum in human peripheral blood mononuclear cells from healthy individuals and those from patients with multiple sclerosis in vitro. Dendrocrumenol B (2) and dendrocrumenol D (4) showed strong immunomodulatory effects on both CD3+ T cells and CD14+ monocytes. Compounds 2 and 4 could reduce IL-2 and TNF production in T cells and monocytes that were treated with phorbol-12-myristate-13-acetate and ionomycin (PMA/Iono). Deep immune profiling using high-dimensional single-cell mass cytometry could confirm immunomodulatory effects of 4, quantified by the reduction of activated T cell population under PMA/Iono stimulation, in comparison to the stimulated T cells without treatment.

In vitro and in silico studies of 7'',8''-buddlenol D anti-inflammatory lignans from Carallia brachiata as p38 MAP kinase inhibitors.

Excessive macrophage activation induces the release of high levels of inflammatory mediators which not only amplify chronic inflammation and degenerative diseases but also exacerbate fever and retard wound healing. To identify anti-inflammatory molecules, we examined Carallia brachiata-a medicinal terrestrial plant from Rhizophoraceae. Furofuran lignans [(-)-(7''R,8''S)-buddlenol D (1) and (-)-(7''S,8''S)-buddlenol D (2)] isolated from the stem and bark inhibited nitric oxide (half maximal inhibitory concentration (IC50): 9.25 ± 2.69 and 8.43 ± 1.20 micromolar for 1 and 2, respectively) and prostaglandin E2 (IC50: 6.15 ± 0.39 and 5.70 ± 0.97 micromolar for 1 and 2, respectively) productions in lipopolysaccharide-induced RAW264.7 cells. From western blotting, 1 and 2 suppressed LPS-induced inducible nitric oxide synthase and cyclooxygenase-2 expression in a dose-dependent manner (0.3-30 micromolar). Moreover, analysis of the mitogen-activated protein kinase (MAPK) signaling pathway showed decreased p38 phosphorylation levels in 1- and 2-treated cells, while phosphorylated ERK1/2 and JNK levels were unaffected. This discovery agreed with in silico studies which suggested 1 and 2 bound to the ATP-binding site in p38-alpha MAPK based on predicted binding affinity and intermolecular interaction docking. In summary, 7'',8''-buddlenol D epimers demonstrated anti-inflammatory activities via p38 MAPK inhibition and may be used as viable anti-inflammatory therapies.

Metal-Decorated InN Monolayer Senses N2 against CO2.

Poor selectivity is a common problem faced by gas sensors. In particular, the contribution of each gas cannot be reasonably distributed when a binary mixture gas is co-adsorbed. In this paper, taking CO2 and N2 as an example, density functional theory is used to reveal the mechanism of selective adsorption of a transition metal (Fe, Co, Ni, and Cu)-decorated InN monolayer. The results show that Ni decoration can improve the conductivity of the InN monolayer while at the same time demonstrating an unexpected affinity for binding N2 instead of CO2. Compared with the pristine InN monolayer, the adsorption energies of N2 and CO2 on the Ni-decorated InN are dramatically increased from -0.1 to -1.93 eV and from -0.2 to -0.66 eV, respectively. Interestingly, for the first time, the density of states demonstrates that the Ni-decorated InN monolayer achieves a single electrical response to N2, eliminating the interference of CO2. Furthermore, the d-band center theory explains the advantage of Ni decorated in gas adsorption over Fe, Co, and Cu atoms. We also highlight the necessity of thermodynamic calculations in evaluating practical applications. Our theoretical results provide new insights and opportunities for exploring N2-sensitive materials with high selectivity.

Eight Indole Alkaloids from the Roots of Maerua siamensis and Their Nitric Oxide Inhibitory Effects.

Maerua siamensis (Capparaceae) roots are used for treating pain and inflammation in traditional Thai medicine. Eight new indole alkaloids, named maeruanitriles A and B, maeroximes A-C, and maeruabisindoles A-C, were isolated from them. Spectroscopic methods and computational analysis were applied to determine the structure of the isolated compounds. Maeroximes A-C possesses an unusual O-methyloxime moiety. The bisindole alkaloid maeruabisindoles A and B possess a rare azete ring, whereas maeruabisindole C is the first indolo[3,2-b]carbazole derivative found in this plant family. Five compounds [maeruanitriles A and B, maeroxime C, maeruabisindoles B, and C] displayed anti-inflammatory activity by inhibiting nitric oxide (NO) production in the lipopolysaccharide-induced RAW 264.7 cells. Maeruabisindole B was the most active inhibitor of NO production, with an IC50 of 31.1 ± 1.8 µM compared to indomethacin (IC50 = 150.0 ± 16.0 µM) as the positive control.

New acylphloroglucinols from a crude acetone extract of Eucalyptus camaldulensis Dehnh. leaf.

Acylphloroglucinols are well-known Eucalyptus secondary metabolites which exhibit a variety of structures and bioactivities. The investigation of a crude acetone extract of Eucalyptus camaldulensis leaves led to the isolation of two new acylphloroglucinols, eucalypcamals O and P (1 and 2) together with seven phloroglucinols (3-9), and a benzene derivative (10). Their chemical structures were elucidated by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy and mass spectroscopy. The absolute configurations of compounds 1 and 2 were established by comparison of experimental and calculated electronic circular dichroism (ECD) data. In the putative biosynthetic pathway, eucalypcamals O and P should be derived from hetero-Diels-Alder reaction between grandinol and trans-isoeugenol.

Phloroglucinol-meroterpenoids from the leaves of Eucalyptus camaldulensis Dehnh.

Fourteen undescribed phloroglucinol-meroterpenoids, namely eucalypcamals A-N, were isolated from a CH2Cl2 extract of the leaves of Eucalyptus camaldulensis Dehnh. In addition, from the same extract, twelve known phloroglucinols, three known flavonoids, and four known phenolic compounds were also isolated. The structures of the undescribed compounds were analyzed by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, and high resolution electrospray ionization mass spectrometry (HRESIMS). The assignments of the absolute configurations were performed by comparing the experimental electronic circular dichroism (ECD) data with the calculated values. Eucalyprobusal E was found to be cytotoxic against HCT116, Jurkat, and MDA-MB-231 cell lines with IC50 values of 17.6, 9.44, and 17.9 µM, respectively. Eucalrobusone F exhibited antibacterial activity against methicillin-resistant S. aureus (MRSA) and S. aureus with minimum inhibitory concentration/minimum bactericidal concentration (MIC/MBC) values of 4/4 µg/mL while euglobal Ia1 showed antifungal activity with MIC/MFC values of 16/16 µg/mL.