Comprehensive Spectral Analyses Research Articles

Artemordins A—S, Cadinane‐Type Sesquiterpenoid Dimers from Artemisia ordosica and Their Antihepatoma Activities

Comprehensive SummaryNineteen new cadinane‐involving sesquiterpenoid dimers, artemordins A—S (1—19), together with 13 known SDs (20—32) were isolated from Artemisia ordosica. Their structures and absolute configurations were established by comprehensive spectral analyses, X‐ray single crystal diffraction, theoretical ECD, and NMR calculations. Chemically, artemordins A—F (1—6) were the first examples of two cadinane units constructed by unprecedented C‐3−C‐15′ or C‐3−C‐13′ single bond with an oxido‐rearranged 6/5/6/6 fused ring system; artemordins G—K (7—11) were biogenetically connected by [4 + 2] cycloaddition reaction and artemordins G—J (7—10) possessed a novel 5/6/6/6/6/6/5‐heptacyclic fused ring system. Artemordins L—S (12—19) were formed by esterification, which involved three different types of sesquiterpenoids. Antihepatoma assay suggested that the most active compounds, artemordins B and H (2 and 8), exhibited inhibitory activities on three hepatoma cell lines with IC50 values of 26.9 and 25.1 μmol/L (HepG2), 29.5 and 18.3 μmol/L (Huh7), 19.7 and 15.7 μmol/L (SK‐Hep‐1).

Atomically dispersed Mn sites on TiO2(B) microspheres enables efficient photocatalytic abatement of NOx

While photocatalytic technology has been recognized as an effective means for removing low-concentration NOx in ambient atmosphere, it still faces the challenge of the deep oxidation in high efficiency. In many cases, the release of more toxic NO2 byproduct appeared to be inevitable during the photocatalytic oxidation of NO. Herein we report that the atomically dispersed MnOx cocatalyst on TiO2(B) microspheres could significantly enhance the deep oxidation of NOx under mild photocatalytic conditions (1 mW/cm2 UV-A light, 1 L/min flow rate). At an initial NO concentration of 0.35 ppm, ca. 67.15% of NO is oxidized on the MT-0.5 sample, which is 2.76 times higher than the pristine TiO2(B) sample. More importantly, the release of NO2 is suppressed by 2.11 times. Comprehensive spectral analyses suggest that atomically dispersed MnOx effectively promotes the charge separation of photogenerated carriers in TiO2(B), even better than MnOx nanoparticles-loaded TiO2(B). EPR and in-situ FTIR analyses illustrate that atomically dispersed MnOx-loaded TiO2(B) sample exhibits excellent low concentration NOx abatement performance, thus providing a rational mechanism for the NO deep oxidation pathway. This study not only provides a unique approach for preparing non-noble metal atomically dispersed co-catalysts, but also affords an effective means for efficient photocatalytic NO degradation.

New Glycerolipids from the Traditional Chinese Medicine of Syngnathus acus (Hai-Long).

Two new glycerolipids, syngaculipids A and B (1 and 2), one first naturally occurring metabolite (8), together with five known compounds (3-7) were isolated from the AcOEt fraction of Syngnathus acus L. (Hai-Long). Their structures were elucidated by comprehensive spectral analyses involving UV, IR, MS, 1D and 2D NMR spectra and ECD calculations. All the isolated compounds were evaluated for their cytotoxicity against A549 and HCT-116 cell lines. Compound 8 exhibited moderate cytotoxicity with IC50 values of 34.5 and 38.9 μM on the A549 and HCT-116 cell lines, respectively.

Bisabolane-type sesquiterpenoids with potential anti-inflammatory and anti-HIV activities from the stems and leaves of Morinda citrifolia

The phytochemical study on the stems and leaves of Morinda citrifolia L. resulted in the isolation of a new naturally occurring bisabolane-type sesquiterpenoid, morincitrinoid A (1), together with five known analogues (2–6). The chemical structure of 1 was elucidated by comprehensive spectral analyses. The known compounds 2–6 were identified by comparing their spectral data with those reported in the literature, which were isolated from M. citrifolia for the first time. In addition, the anti-inflammatory and anti-HIV activities of compounds 1–6 were evaluated in vitro. Compounds 1–6 displayed significant inhibitory activities on NO (nitric oxide) production induced by lipopolysaccharide in mouse macrophage RAW 264.7 cells with IC50 values ranging from 0.98 ± 0.07 to 6.32 ± 0.11 μM, which was comparable to hydrocortisone. Meanwhile, compounds 1–6 showed remarkable anti-HIV-1 reverse transcriptase (RT) effects with the EC50 values ranging from 0.16 to 6.29 μM.

Artemidubolides A−T, cytotoxic unreported guaiane-type sesquiterpenoid dimers against three hepatoma cell lines from Artemisia dubia

A random bioassay revealed that the EtOH extract and EtOAc fraction of Artemisia dubia Wall. (Asteraceae) exhibited cytotoxic activity against HepG2 cells with inhibitory ratios of 57.1% and 84.2% at a concentration of 100.0 μg/mL. Bio-guided isolation combined by LC-MS-IT-TOF analyses of the active fractions led to the isolation of 20 previously undescribed guaiane-type sesquiterpenoid dimers named artemidubolides A−T (1–20). Their structures and the absolute configurations were determined by comprehensive spectral analyses, comparison of the experimental and calculated ECD spectra, and seven compounds (artemidubolides A, B, D, F, K, O and R) were confirmed unequivocally by single crystal X-ray diffraction analysis. Structurally, artemidubolides A–Q were [4 + 2] Diels–Alder adducts of two monomeric guaianolides, and artemidubolides R–T were linked though an ester bond. All the isolated compounds were evaluated for their hepatomatic cytotoxicity against HepG2, Huh7, and SK-Hep-1 cell lines to demonstrate that 18 compounds exhibited obvious cytotoxicity against three tested hepatoma cell lines with IC50 values in the range of 5.4–87.6 μM. Importantly, artemidubolides B, D, and M exhibited hepatoma cytotoxicity with IC50 values of 5.4, 5.7, and 9.7 (HepG2), 8.2, 4.3, and 12.2 (Huh7), and 13.4, 8.4, and 12.9 μM (SK-Hep-1), respectively. Mechanism investigation in HepG2 cells suggested the most active artemidubolide D dose-dependently inhibited cell migration and invasion, induced G1/M cell cycle arrest by down-regulating proteins CDK4, CDK6 and CyclinD1 and up-regulating the level of protein P21; and induced apoptosis by down-regulated of PARP-1 and BCL-2 expression and up-regulating Bax and cleaved PARP-1 levels.

Oxygen-containing groups in cellulose and lignin biochar: their roles in U(VI) adsorption.

The adsorption behaviors of cellulose and lignin biochar depend on the evolution of their oxygen-containing groups to some extent. In this study, cellulose-rich pakchoi and lignin-rich corncob were selected to prepare the pyrolytic biochar at variable temperatures, named PBC and CBC, respectively. Their structure-function relationships were in-depth studied via the combination of the adsorption experiments of U(VI) and comprehensive spectral analyses. The maximal adsorption capacity of PBC 300, obtained at 300°C, was measured as 46.62mgg-1 for U(VI), which was ⁓1.3 times higher than 35.60mgg-1 of CBC 300. U(VI) adsorption on PBC and CBC were predominantly ascribed to the coordination interaction between oxygen-containing groups and U(VI). Interestingly, the main complexation groups were distinct in both biochars due to the different inherent evolutions of cellulose and lignin. Volatile d-glucose chains in cellulose were apt to degrade rapidly, and the formed carboxyls acted as the most important sites in PBC. However, the stable aromatic network in lignin led to a slow degradation, and more hydroxyls thus remained in CBC, which controlled U(VI) adsorption. In this study, we obtained greatly cost-effective adsorbents of U(VI) and provided some essential insights into understanding the structural evolution-function relationship of cellulose and lignin biochar.

Prenylated chromones and flavonoids from Artocarpus heterophyllus with their potential antiproliferative and anti-inflammatory activities

Two new prenylated chromones, artoheterophines A (1) and B (2), five known prenylated chromones (3–7), as well as five known biogenetically related prenylated flavonoids (8–12) were isolated and characterized from the stems and leaves of A. heterophyllus. Their chemical structures were unambiguously determined through comprehensive spectral data analyses. The antiproliferative and anti-inflammatory effects of all these isolated prenylated chromones and flavonoids were evaluated in vitro. As a result, compounds 1–12 showed notable inhibitory effects against various human cancer cell lines with IC50 values ranging from 0.36 ± 0.02 to 22.09 ± 0.16 μM. Meanwhile, compounds 1–12 exhibited significant inhibitory activities on nitric oxide (NO) production holding IC50 values in the range of 0.48 ± 0.05–19.87 ± 0.21 µM. These research results suggest that the isolation and characterization of these prenylated chromones (1–7) and flavonoids (8–12) holding significant antiproliferative and anti-inflammatory activities could be significant to the discovery and development of new natural anti-tumor and anti-inflammatory drugs. The findings also provides a phytochemical evidence for further development and utilization of the stems and leaves of A. heterophyllus in health and pharmaceutical products.

Bioactive prenylated coumarins as potential anti-inflammatory and anti-HIV agents from Clausena lenis.

The phytochemical study on the stems of Clausena lenis resulted in the isolation of three new prenylated coumarins, clauselenins A-C (1-3), together with nine known prenylated coumarins (4-12). The chemical structures of new prenylated coumarins (1-3) were elucidated by means of comprehensive spectral analyses and the known compounds (4-12) were determined by means of comparing their experimental spectral data with those described data in the literatures. All isolated prenylated coumarins were assessed for their anti-inflammatory effects together with anti-HIV activities in vitro. Prenylated coumarins 1-12 displayed remarkable inhibitory effects against nitric oxide (NO) production induced by lipopolysaccharide in mouse macrophage RAW 264.7 cells in vitro with the IC50 values which are comparable to hydrocortisone. Meanwhile, prenylated coumarins 1-12 exhibited considerable anti-HIV-1 reverse transcriptase (RT) activities possessing EC50 values in the range of 0.17-9.08µM. These findings indicate that the isolation and identification of these prenylated coumarins with pronounced anti-inflammatory effects as well as anti-HIV activities separated from the stems of C. lenis could be of great significance to the development of new anti-inflammatory and anti-HIV agents and their potential applications in the pharmaceutical industry.

A comparative study on the structural features of humic acids extracted from lignites using comprehensive spectral analyses.

The lignite reserves of Zhaotong and Mile in China are abundant and lignite utilizations are limited, however, humic acids (HAs) extracted from lignites play a significant role in many fields including agriculture, environmental protection and so on. Herein, the structures of HAs extracted from Zhaotong and Mile lignites (denoted as ZLHA and MLHA, respectively) were characterized and compared to each other using comprehensive spectral analyses. As a result, the UV-Vis spectrum analyses of HAs indicated that the molecular weight of MLHA is larger than that of ZLHA. Cross polarization magic angle spinning 13C NMR, which is rarely used to analyze the structures of HAs using fitting peaks, and FT-IR spectrum analyses indicated that both the aromaticity and the oxygen-containing group contents of ZLHA are higher than those of MLHA, and the HAs' aromaticity could be confirmed by the results of the X-ray diffraction patterns. Additionally, the main existing forms of the elements in the HAs were obtained from X-ray photoelectron spectrum analyses, which are not commonly used for HA analyses. In this work, the utilization of comprehensive spectral analyses was an effective method to study the structural features of ZLHA and MLHA and it could provide a basic reference for the applications of ZLHA and MLHA.

Geranylated carbazole alkaloids with potential neuroprotective activities from the stems and leaves of Clausena lansium

Clausena lansium (Lour.) Skeels is an evergreen small tree or shrub with great economic value, which belongs to the genus Clausena of the Rutaceae family. C. lansium is indigenous to Southern China, while currently widely cultivated in subtropical and tropical regions not only for the nutritional value and pharmacological uses of its fruits but also as a medicinal and ornamental plant. In this study, a systematic phytochemical study on the stems and leaves of C. lansium caused the separation and identification of two new geranylated carbazole alkaloids, clauselansiumines A (1) and B (2), as well as 10 known geranylated carbazole alkaloids (3–12). The chemical structures of these isolated geranylated carbazole alkaloids (1–12) were unambiguously determined based on comprehensive spectral data analyses. All these isolated geranylated carbazole alkaloids were tested for their neuroprotective effects against 6-hydroxydopamine induced cell death in human neuroblastoma SH-SY5Y cells in vitro. Compounds 1–12 displayed remarkable neuroprotective effects holding the EC50 values ranging from 0.48 ± 0.04 to 12.36 ± 0.16 μM. These research results disclosed that the separation and purification of these geranylated carbazole alkaloids possessing remarkable neuroprotective effects separated from C. lansium could be extremely important to the discovery of new agents for the treatment and prevention for Parkinson's disease.

The Galactic WN stars revisited

Comprehensive spectral analyses of the Galactic Wolf-Rayet stars of the nitrogen sequence (i.e. the WN subclass) have been performed in a previous paper. However, the distances of these objects were poorly known. Distances have a direct impact on the “absolute” parameters, such as luminosities and mass-loss rates. The recent Gaia Data Release (DR2) of trigonometric parallaxes includes nearly all WN stars of our Galactic sample. In the present paper, we apply the new distances to the previously analyzed Galactic WN stars and rescale the results accordingly. On this basis, we present a revised catalog of 55 Galactic WN stars with their stellar and wind parameters. The correlations between mass-loss rate and luminosity show a large scatter, for the hydrogen-free WN stars as well as for those with detectable hydrogen. The slopes of the log L − log Ṁ correlations are shallower than found previously. The empirical Hertzsprung–Russell diagram (HRD) still shows the previously established dichotomy between the hydrogen-free early WN subtypes that are located on the hot side of the zero-age main sequence (ZAMS), and the late WN subtypes, which show hydrogen and reside mostly at cooler temperatures than the ZAMS (with few exceptions). However, with the new distances, the distribution of stellar luminosities became more continuous than obtained previously. The hydrogen-showing stars of late WN subtype are still found to be typically more luminous than the hydrogen-free early subtypes, but there is a range of luminosities where both subclasses overlap. The empirical HRD of the Galactic single WN stars is compared with recent evolutionary tracks. Neither these single-star evolutionary models nor binary scenarios can provide a fully satisfactory explanation for the parameters of these objects and their location in the HRD.

Investigating state transition luminosities of Galactic black hole transients in the outburst decay

Abstract We have performed a comprehensive spectral and timing analyses of Galactic black hole transients (GBHTs) during outburst decay in order to obtain the distribution of state transition luminosities. Using the archival data of the Rossi X-ray Timing Explorer (RXTE), we have calculated the weighted mean for state transition luminosities of 11 BH sources in 19 different outbursts and for disc and power law luminosities separately. We also produced histograms of these luminosities in terms of Eddington luminosity fraction (ELF) and fitted them with a Gaussian. Our results show the tightest clustering in bolometric power law luminosity with a mean logarithmic ELF of −1.70 ± 0.21 during the index transition (as the photon index starts to decrease towards the hard state). We obtained mean logarithmic ELF of −1.80 ± 0.25 during the transition to the hard state (as the photon index reaches the lowest value) and −1.50 ± 0.32 for disc-blackbody luminosity (DBB) during the transition to the hard-intermediate state (HIMS). We discussed the reasons for clustering and possible explanations for sources that show a transition luminosity significantly below or above the general trends.

Observation of an anti-PT-symmetric exceptional point and energy-difference conserving dynamics in electrical circuit resonators

Parity-time (PT) symmetry and associated non-Hermitian properties in open physical systems have been intensively studied in search of new interaction schemes and their applications. Here, we experimentally demonstrate an electrical circuit producing key non-Hermitian properties and unusual wave dynamics grounded on anti-PT (APT) symmetry. Using a resistively coupled amplifying-LRC-resonator circuit, we realize a generic APT-symmetric system that enables comprehensive spectral and time-domain analyses on essential consequences of the APT symmetry. We observe an APT-symmetric exceptional point (EP), inverse PT-symmetry breaking transition, and counterintuitive energy-difference conserving dynamics in stark contrast to the standard Hermitian dynamics keeping the system’s total energy constant. Therefore, we experimentally confirm unique properties of APT-symmetric systems, and further development in other areas of physics may provide new wave-manipulation techniques and innovative device-operation principles.

NuSTAR and XMM-Newton Observations of the 2015 Outburst Decay of GX 339-4

Abstract The extent of the accretion disk in the low/hard state of stellar mass black hole X-ray binaries remains an open question. There is some evidence suggesting that the inner accretion disk is truncated and replaced by a hot flow, while the detection of relativistic broadened iron emission lines seems to require an accretion disk extending fully to the innermost stable circular orbit. We present comprehensive spectral and timing analyses of six Nuclear Spectroscopic Telescope Array and XMM-Newton observations of GX 339–4 taken during outburst decay in the autumn of 2015. Using a spectral model consisting of a thermal accretion disk, Comptonized emission, and a relativistic reflection component, we obtain a decreasing photon index, consistent with an X-ray binary during outburst decay. Although we observe a discrepancy in the inner radius of the accretion disk and that of the reflector, which can be attributed to the different underlying assumptions in each model, both model components indicate a truncated accretion disk that resiles with decreasing luminosity. The evolution of the characteristic frequency in Fourier power spectra and their missing energy dependence support the interpretation of a truncated and evolving disk in the hard state. The XMM-Newton data set allowed us to study, for the first time, the evolution of the covariance spectra and ratio during outburst decay. The covariance ratio increases and steeps during outburst decay, consistent with increased disk instabilities.

The metallicity dependence of WR winds

AbstractWolf-Rayet (WR) stars are the most advanced stage in the evolution of the most massive stars. The strong feedback provided by these objects and their subsequent supernova (SN) explosions are decisive for a variety of astrophysical topics such as the cosmic matter cycle. Consequently, understanding the properties of WR stars and their evolution is indispensable. A crucial but still not well known quantity determining the evolution of WR stars is their mass-loss rate. Since the mass loss is predicted to increase with metallicity, the feedback provided by these objects and their spectral appearance are expected to be a function of the metal content of their host galaxy. This has severe implications for the role of massive stars in general and the exploration of low metallicity environments in particular. Hitherto, the metallicity dependence of WR star winds was not well studied. In this contribution, we review the results from our comprehensive spectral analyses of WR stars in environments of different metallicities, ranging from slightly super-solar to SMC-like metallicities. Based on these studies, we derived empirical relations for the dependence of the WN mass-loss rates on the metallicity and iron abundance, respectively.

α-Pyrones with Diverse Hydroxy Substitutions from Three Marine-Derived Nocardiopsis Strains.

Eight new α-pyrones 1-8 and three known α-pyrones 9-11 were isolated from three marine-derived Nocardiopsis strains SCSIO 10419, SCSIO 04583, and SCSIO KS107. The structures of compounds 1-8 were elucidated by comprehensive spectral analyses. The absolute configurations of 4-deoxyphomapyrone C (1), 4-deoxy-11-hydroxyphomapyrone C (3), 4-deoxy-7R-hydroxyphomapyrone C (5), and phomapyrone C (11) were determined by TDDFT-ECD calculations for the solution conformers, which revealed that the conformation of the side chain was decisive for the sign of the characteristic high-wavelength ECD transition. (-)-4-Deoxy-8-hydroxyphomapyrone C (4) was isolated from SCSIO 10419 and was deduced as a diastereomeric mixture containing (8S)- and (8R)-4-deoxy-8-hydroxyphomapyrone C in a ratio of 2.6:1 (8R:8S), by chiral-phase HPLC analysis and Mosher's ester analysis. Interestingly, 7-hydroxymucidone (9) was isolated from both SCSIO 04583 and SCSIO KS107, as an enantiomeric mixture containing (7S)-hydroxymucidone (major in 9 from SCSIO 04583) and (7R)-hydroxymucidone (major in 9 from SCSIO KS107). α-Pyrones 3-5 were identified as three isomers of phomapyrone C (11) with diverse hydroxy substitutions. α-Pyrones 10-hydroxymucidone (6), 4-hydroxymucidone (8), and 9, differed in the position of the hydroxy group. Several α-pyrones exhibited moderate growth inhibitory activity against Micrococcus luteus and Bacillus subtilis.

Defect-Induced Yellow Color in Nb-Doped TiO2 and Its Impact on Visible-Light Photocatalysis

Doping TiO2 photocatalysts with foreign ions has been deemed an effective method to enhance visible light absorption and thus increase their photocatalytic performance. Herein, we report that Nb-doped TiO2 porous microspheres prepared by ultrasonic spray pyrolysis of peroxide precursor solution are yellow, and the yellow coloration becomes increasingly conspicuous with increasing Nb dopant concentration. Comprehensive spectral analyses show that both surface peroxo species and bulk Ti3+ are introduced into TiO2 microsphere samples together by charge compensation with Nb5+ dopant and are responsible for the coloration of TiO2. The Nb-doped microspheres show higher photocatalytic rates than undoped TiO2 for the degradation of gaseous acetaldehyde under visible irradiation but slower rates under ultraviolet light. Moreover, the photocatalytic mineralization rates of acetaldehyde to CO2 are lowered with Nb doping under both visible and UV irradiation. Correlation between the results of surface photovoltage sp...

Sesquiterpenoids and 2‐(2‐Phenylethyl)‐4H‐chromen‐4‐one (=2‐(2‐Phenylethyl)‐4H‐1‐benzopyran‐4‐one) Derivatives from Aquilaria malaccensis Agarwood

AbstractThe four new sesquiterpenoids 1–4, and the new 2‐(2‐phenylethyl)‐4H‐chromen‐4‐one (=2‐(2‐phenylethyl)‐4H‐1‐benzopyran‐4‐one) derivative 5, together with the two known sesquiterpenoids 6 and 7, the five known chromenones 8–12, and 1‐hydroxy‐1,5‐diphenylpentan‐3‐one (13), were isolated from a 70% MeOH extract of Aquilaria malaccensis agarwood chips. Their structures were elucidated on the basis of comprehensive spectral analyses and comparison with literature data.

Origins of device performance in dicarboxyterpyridine Ru(ii) dye-sensitized solar cells

This study carefully examines carrier dynamics in highly efficient dye-sensitized solar cells (DSSCs) based on a series of recently developed dicarboxyterpyridine Ru(II) dyes (PRT-11-15). Comprehensive spectral response analyses, transient photovoltage and photocurrent measurements, and transient absorption techniques are exploited to investigate the effects of various functionalized terpyridines on carrier injection efficiency (η(inj)), electron diffusion length (L) and dye-regeneration efficiency (η(reg)). The resulting parameters are fully comprehended, which are then correlated with the origins of the device performance such as short circuit current density J(sc), open circuit voltage V(oc) and hence the overall conversion efficiency η in these Ru(II) based DSSCs.

Spectroscopic analysis of Cr,Er:Gd 3Ga 5O 12 crystals as candidates of potential xenon lamp pumped ~ 2.7 μm laser

A series of Cr,Er:Gd 3Ga 5O 12 crystals with high concentrations of Er 3 + were grown by Czochralski method. The absorption spectra, the up-conversion, near infrared (NIR) and mid-infrared (Mid-IR) luminescence spectra as well as the luminescence decay curves of Er: 4I 13/2 and 4I 11/2 levels were measured at room temperature. The spectroscopic properties of Cr,Er:Gd 3Ga 5O 12 crystals and Cr–Er energy transfer processes were investigated. The spectroscopy of the Er 3 + : 4I 11/2 → 4I 13/2 transition was centralized to discuss, and the important optical parameters including luminescence lifetimes and the Cr–Er energy transfer efficiency are presented. Based on the comprehensive spectral analyses, 0.6 at.%Cr/50 at.%Er:GGG crystal is preferred as candidate of potential xenon lamp pumped ~ 2.7 μm laser in this work.