High-resolution Electrospray Ionization Mass Spectrometry Research Articles

Mining of Meroterpenoids with Anti-inflammatory Activity from the Mangrove Endophytic Fungus Talaromyces sp. JNQQJ-4 by Genome Analysis and Molecular Network Strategy.

Talaromeroterpenoids A-G (1-7), seven new 3,5-dimethylorsellinic-acid-derived meroterpenoids, and two known analogues (8 and 9) were isolated from the mangrove endophytic fungus Talaromyces sp. JNQQJ-4 by genome analysis and a molecular networking strategy. Their structures and absolute configurations were established by nuclear magnetic resonance data, high-resolution electrospray ionization mass spectrometry, and X-ray diffraction. Compound 1 possesses an unprecedented rearrangement 7/6/6/5/5/5 hexacyclic skeleton based on a 2,8,18,21-tetraoxa-hexacyclo-[12.5.2.13,12.01,16.04,10.016,22]docosane core. In bioassays, compound 2 exhibited promising anti-inflammatory activity by suppressing the expression of pro-inflammatory factors and inactivating the NF-κB signaling pathway.

Quantum-mechanics-based structural analysis of phenolic glycosides from Cuscuta japonica seeds with protective effects against H2O2-induced oxidative stress in SH-SY5Y cells.

Japanese dodder (Cuscuta japonica Choisy) is a parasitic plant with diverse pharmaceutical properties that has demonstrated great promise for the development of dietary supplements and herbal medicines. A systematic phytochemical investigation of dodder seeds yielded 12 previously undescribed aromatic glycosides (1-12) and eight known constituents (13-20) from various groups, including phenolics, flavonoids, and lignan glycosides. Compound structures were determined using a combination of high-resolution electrospray ionization mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. Moreover, quantum-mechanics-driven 1H iterative full spin analysis revealed intricate NMR spectral details for the isolated glycosides, including multiplicities and coupling constants that were previously ambiguous, providing crucial insight into the presence of higher-order resonance effects in the sugar units as well as long-range couplings in unsaturated molecules. Furthermore, the abilities of the plant extract as well as compounds 1, 2, 4-7, 10, 11, and 14-20 to restore cell viability and reduce reactive oxygen species production in SH-SY5Y cells suggest that C. japonica and its isolates are potential antioxidant neuroprotective therapeutic candidates.

Structural Changes in Atomically Precise Ag29 Nanoclusters upon Sequential Attachment and Detachment of Secondary Ligands.

Elucidating the structural dynamics of ligand-stabilized noble metal nanoclusters (NCs) is critical for understanding their properties and for developing applications. Ligand rearrangement at NC surfaces is an important contributor to structural change. In this study, we investigate the dynamic behavior of ligand-protected [Ag29(L)12]3- NC's (L = 1,3-benzenedithiol) interacting with secondary ligand 2,2'-[1,4-phenylenebis (methylidynenitrilo)] bis[benzenethiol] (referred to as L'). We specifically focus on the structural characteristics of NC-based adducts [Ag29(L)12]L'n3- where n ranges from 1 to 4. This is probed experimentally by using a combination of ultraviolet-visible (UV-vis) spectroscopy, high-resolution electrospray ionization mass spectrometry (ESI MS), and ion mobility mass spectrometry (IM MS) coupled with collision-induced dissociation (MS2 IMS). Density functional theory (DFT) calculations infer comparatively weak noncovalent interactions between the NCs and attached secondary ligands consistent with the fragmentation behavior and experimentally determined collision cross-sections (CCSs), which show a monotonic CCS increase of [Ag29(L)12]L'n3- with an increasing number of L' (n = 1-4). From a detailed analysis of the predicted structures, we infer progressive expansion of the Ag-S staple framework of the precursor NC as secondary ligands are added. Interestingly, detachment of L' from gas-phase [Ag29(L)12]L'n3- by collisional heating yields structures which retain "footprints" of the detached secondary ligands on a millisecond time scale.

The effects of ultra-selective beta1-antagonism on the metabolic and cytokine profile in septic shock patients receiving noradrenaline: a sub-investigation from the STRESS-L Randomised Study

PurposeThe landiolol and organ failure in patients with septic shock (STRESS-L study) included a pre-planned sub-study to assess the effect of landiolol treatment on inflammatory and metabolomic markers.MethodsSamples collected from 91 patients randomised to STRESS-L were profiled for immune and metabolomic markers. A panel of pro- and anti-inflammatory cytokines were measured through commercially acquired multiplex Luminex assays and statistically analysed by individual and cluster-level analysis (patient). Metabolite fingerprinting was carried out by flow infusion electrospray ionisation high-resolution mass spectrometry and metabolomic data were analysed using the R-based platform MetaboAnalyst. The metabolites were identified using DIMEdb (dimedb.ibers.aber.ac.uk) from their mass/charge ratios. These metabolomic data were also re-analysed using individual and cluster-level analysis. The individual-level models were adjusted for confounders, such as age, sex, noradrenaline dosage and patient (random effect).ResultsAnalysis was undertaken at cluster- and individual-level. There were no significant differences in cytokine concentration level between trial arms nor survivors and non-survivors over the duration of the observations from day 1 to day 4. Metabolomic analysis showed some separation in the levels of ceramides and cardiolipins between those who survived and those who died. Following adjusted analysis for confounders, plasma metabolite concentrations remained statistically different between landiolol and standard care arms for succinic acid, l-tryptophan, l-alanine, 2,2,2-trichloroethanol, lactic acid and d-glucose.ConclusionsIn a study of ICU patients with established septic shock and a tachycardia, landiolol treatment used to reduce the heart rate from above 95 to a range between 80 and 94 beats per minute did not induce significant cytokine changes. d-Glucose, lactic acid, succinic acid, l-alanine, l-tryptophan and trichloroethanol were pathways that may merit further investigation.Trial Registration: EU Clinical Trials Register Eudra CT: 2017-001785-14 (https://www.clinicaltrialsregister.eu/ctr-search/trial/2017-001785-14/GB); ISRCTN registry Identifier: ISRCTN12600919 (https://www.isrctn.com/ISRCTN12600919).

Ellagitannins From Pomegranate Flower With Whitening and Anti-Skin Photoaging Effect.

A new depside glucoside rosarugoside E (1), together with four known compounds punicalagin (2), corilagin (3), granatin B (4), and ellagic acid (5) were isolated from the ethanol extract of pomegranate (Punica granatum L.) flower. Their structures were identified based on careful analysis of various spectral data including ultraviolet, infrared, high-resolution electrospray ionization-mass spectrometry, and 1D and 2D nuclear magnetic resonance. The whitening and anti-aging effects of all compounds were evaluated based on the levels of protein and gene. The result displayed that all compounds exhibited inhibitory activity for tyrosinase at maximum safe concentration, except for compound 2. Compounds 3 and 5 exhibited significant inhibitory activity for tyrosinase, indicating their whitening efficacy. The anti-aging activity evaluation assay showed that all compounds could downregulate the expression of the MMP1 gene, decrease the expression of matrix metalloproteinase 1, and increase the content of type 1 collagen at the maximum safe concentration compared with negative control (ultraviolet A irradiation treatment).

Generation of glucosylantimycins by heterologous expression of a promiscuous glycosyltransferase in a deepsea-derived Streptomyces.

Antimycins are a class of depsipeptide compounds that exhibit diverse bioactivities. However, their potential clinical applications are hampered by high cell toxicities. Glycosylation usually has profound impacts on the physicochemical properties, bioactivities and toxicities of natural products. In this study, we overexpressed an artificial glycosyltransferase (GT) gene sbmGT1 in deepsea-derived Streptomyces albus ZH66, leading to the discovery of three new antimycin derivatives glucosylantimycins A, B and C (1-3). Their structures were determined by a combination of spectroscopic methods, including high resolution electrospray ionisation mass spectrometry (HRESIMS) and nuclear magnetic resonance (NMR) analysis. The glycosylation remarkably improved the water solubility but simultaneously reduced the cytotoxicities of antimycins towards human cervix epidermoid carcinoma (HeLa) and human hepatic carcinoma (HepG2) cell lines.

Structurally diverse sesquiterpenoids from Sarcandra glabra and their anti-inflammatory activities.

Fifteen sesquiterpenoids, including five previously undescribed monomers with oxidative rearranged skeletons (sarglabenoids A-E, 1-5) and three previously unreported lindenane [2+2] dimers (sarglabenoids F-H, 6-8), alongside seven related precursors (9-15), were isolated from the root of Sarcandra glabra. The structures of these compounds were elucidated using a combination of high-resolution electrospray ionization mass spectrometry, one-dimensional and two-dimensional nuclear magnetic resonance spectroscopy, the circular dichroism exciton chirality method, electronic circular dichroism, and nuclear magnetic resonance calculations integrated with DP4+ analysis. Compounds 1 and 2 feature an unique 5/5 spiro ring system, which is likely derived from a pinacol rearrangement of precursor 14. Compounds 3 and 4 are seco-C8/9 derivatives formed via Baeyer-Villiger oxidation of precursors 14 and 15, while compounds 6-8 represent the [2+2] dimers of various lindenane monomers (9-13). Notably, compounds 4 and 5 exhibited moderate inhibition of Interleukin-1β production in non-cytotoxic concentration in lipopolysaccharide-induced Tohoku Hospital Pediatrics-1 cells, with IC50 values of 16.28 ± 0.76 μM and 11.32 ± 0.77 μM respectively.

A New Non-Cyanogenic Cyanoglycoside with Promising α-Glycosidase Inhibitory Activity from the Roots of Cordia trichotoma

Three undescribed non-cyanogenic cyanoglycosides, designated as trichotomoside A (1), B (2), and C (3) along with three known ones (4-6) were isolated from the roots of Cordia trichotoma. In addition, miscellaneous compounds such as acid (1’R,3’S,5’R,8’S,2Z,4E)-dihydrophaseic 3’-O-β-D-glycopyranoside (7), N-(2E)-3-[(2S,3R)-2-(4-hydroxy-3-methoxyphenyl)- 3-(hydroxymethyl)-7-methoxy-2,3-dihydro-1-benzofuran5-yl]acryloylglycine (8), syringaldehyde (9), scoparone (10), 12,16-epoxyglobiferin (11), α-cadinol (12), trichotomol (13), and 1-(3’-methoxypropanoyl)-2,4,5-trimethoxybenzene (14) were also isolated. The structures of all compounds were elucidated by an extensive analysis of spectroscopic data (infrared (IR), nuclear magnetic resonance (NMR), and high-resolution electrospray ionization mass spectrometry (HRESIMS)). The non-cyanogenic cyanoglycosides (1-6) were screened for their α-glucosidase inhibitory activities. None of the compounds exhibited antioxidant or xanthine oxidase activity. Compound 3 exhibited considerable inhibitory ability on α-glucosidase, showing a halfmaximal inhibitory concentration (IC50) = 646 ± 69 µmol L-1 close to the standard acarbose (IC50 = 521 ± 23 µmol L-1), demonstrating its promising antidiabetic action.

Brazoide E, a New Alkaloid and Other Compounds from Justicia wasshauseniana (Acanthaceae)

A new alkaloid, named brazoide E (6), three known steroids (campesterol, β-sitosterol, stigmasterol), two glucosides (3-O-β-D-glucopyranosylsitosterol and 3-O-β-D-glucopyranosyl stigmasterol) and sucrose were isolated from the leaves and stems of Justicia wasshauseniana. Their structures were characterized using high-resolution electrospray ionization mass spectrometry (HRESIMS), nuclear magnetic resonance (1D and 2D NMR), and infrared (IR) spectroscopy. To reinforce the structural proposal, an acetylated derivative (6a) was obtained and its data compared to 6. Moreover, circular dichroism spectroscopy (CD) analysis was performed to determine the absolute stereochemistry, time-dependent density functional theory (TD-DFT) at the wB97X-D/def2-TZVP level, adopting functionals M06-2X and wB97X-D and base aug-cc-pVDZ, was employed to confirm the CD analysis.

Dimeric guaianolide sesquiterpenoids from the flowers of Chrysanthemum indicum ameliorate hepatic steatosis through mitigating SIRT1-mediated lipid accumulation and ferroptosis.

Non-alcoholic fatty liver disease (NAFLD) acts as the primary contributor to non-alcoholic steatohepatitis, fibrosis, cirrhosis, and potentially hepatocellular carcinoma. The flowers of Chrysanthemum indicum, a traditional edible medicinal herb, have been widely used in China for more than 2000 years. However, the function of C. indicum in managing NAFLD has seldom been investigated. To reveal the novel active components and underlying mechanisms of C. indicum in treating NAFLD. An MS/MS-based molecular networking-guided strategy was used for the chemical investigation. The structure identification of the new compounds involved high resolution electrospray ionization mass spectrometry (HRESIMS), 1D and 2D nuclear magnetic resonance (NMR) spectra, electronic circular dichroism (ECD), and X-ray crystallographic analysis. The biological evaluation was performed using Nile Red staining, flow cytometry, commercial kits, western blotting, co-immunoprecipitation, isothermal titration calorimetry, cellular thermal shift assay, drug affinity responsive target stability assay, molecular docking, and confocal immunofluorescence. A total of 27 new dimeric sesquiterpenoids, chryindicolides A-Z (1-26) and chrysanthemolide C (27), together with seven known compounds, were isolated from the flowers of C. indicum under the guide of MS/MS-based molecular networking. Among them, compounds 1-7 were rare chlorine-containing guaianolide dimers. Chryindicolide O (15) directly bound and activated the deacetylase Sirtuin 1 (SIRT1) to reduce de novo lipogenesis, enhance fatty acid β-oxidation, and inhibit ferroptosis in palmitic acid and oleic acid (P/O)-induced AML12 hepatocytes. In addition, chryindicolide O significantly ameliorated liver steatosis in high-fat diet-fed zebrafish. Novel guaianolide dimers from C. indicum alleviated hepatic steatosis through mitigating SIRT1-mediated lipid accumulation and ferroptosis, suggesting that they could be further developed as candidates against NAFLD.

Two New α-Glucosidase Inhibitors from Haplophyllum tuberculatum: Inhibition Kinetics and Mechanistic Insights Through in Vitro and in Silico Approaches.

Diabetes is a multifactorial global health disorder marked by unusually high plasma glucose levels, which can lead to serious consequences including diabetic neuropathy, kidney damage, retinopathy, and cardiovascular disease. One effective therapy approach for reducing hyperglycemia associated with type 2 diabetes is to target α-glucosidase, enzymes that catalyze starch breakdown in the intestine. In the current study, two new (1, 2) and nine known (3-11) compounds were isolated from the rutaceous plant Haplophyllum tuberculatum and characterized by extensive nuclear magnetic resonance spectroscopic techniques and high-resolution electrospray ionization mass spectrometry. After structural elucidation, nine compounds were evaluated for their ability to inhibit α-glucosidase, a target for the treatment of type-2 diabetes. Among them, three compounds (7, 5, and 2) exhibited notable inhibition with half-maximal inhibitory concentration (IC50) values of 3.42 ± 0.12, 5.79 ± 0.28, and 6.75 ± 1.18µM, respectively, while the remaining six compounds (1, 3, 4, 6, 8, and 9) had a moderate activity with IC50 values ranging from 12.14 ± 0.35 to 24.60 ± 0.57µM, compared to the standard drug acarbose (IC50 = 875.75 ± 1.24µM). A kinetic study of compounds 5 and 7 exhibited the competitive type of inhibition with Ki values of 4.82 ± 0.0036 and 3.92 ± 0.0062µM, respectively. Furthermore, a structure-based prediction of the compounds' binding mode suggested that these inhibitors fitted exceptionally well within the active site of the target enzyme, α-glucosidase, forming multiple hydrogen and hydrophobic interactions with its active site residues. In conclusion, compounds with potent α-glucosidase inhibitory activity are abundant in nature and can be explored and further developed for treating diabetes mellitus.

Early detection of bacterial pneumonia by characteristic induced odor signatures

IntroductionThe ability to detect pathogenic bacteria before the onsets of severe respiratory symptoms and to differentiate bacterial infection allows to improve patient-tailored treatment leading to a significant reduction in illness severity, comorbidity as well as antibiotic resistance. As such, this study refines the application of the non-invasive Secondary Electrospray Ionization-High Resolution Mass Spectrometry (SESI-HRMS) methodology for real-time and early detection of human respiratory bacterial pathogens in the respiratory tract of a mouse infection model.MethodsA real-time analysis of changes in volatile metabolites excreted by mice undergoing a lung infection by Staphylococcus aureus or Streptococcus pneumoniae were evaluated using a SESI-HRMS instrument. The infection status was confirmed using classical CFU enumeration and tissue histology. The detected VOCs were analyzed using a pre- and post-processing algorithm along with ANOVA and RASCA statistical evaluation methods.ResultsCharacteristic changes in the VOCs emitted from the mice were detected as early as 4–6 h post-inoculation. Additionally, by using each mouse as its own baseline, we mimicked the inherent variation within biological organism and reported significant variations in 25 volatile organic compounds (VOCs) during the course of a lung bacterial infection.Conclusionthe non-invasive SESI-HRMS enables real-time detection of infection specific VOCs. However, further refinement of this technology is necessary to improve clinical patient management, treatment, and facilitate decisions regarding antibiotic use due to early infection detection.

Anti-Inflammatory Activities of New Compounds Isolated from the Fruits of Foeniculum Vulgare Mill.

Forty-nine compounds, including six previously unknown together with forty-three known ones, were isolated from the fruits of Foeniculum vulgare Mill. Their structures were elucidated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV), nuclear magnetic resonance (NMR), and electronic circular dichroism (ECD) methods. All isolates were evaluated their anti-inflammatory activity. The results indicated that compounds 1 and 6 inhibit lipopolysaccharide (LPS)-induced nitric oxide production in RAW 264.7 macrophages with IC50 values of 41.77±1.80, 46.72±1.75 μmol/L, respectively. Moreover, the potential targets of the four active ingredients were explored through network pharmacology, revealing that SRC, TP53, AKT1, and PIK3CA may serve as key anti-inflammatory targets. Additionally, the anti-inflammatory activities of compounds 1-6 were first observed in this experiment.

Assessment of the Chemical Diversity and Functional Properties of Secondary Metabolites from the Marine Fungus Asteromyces cruciatus.

Natural compounds derived from microorganisms, especially those with antioxidant and anticancer properties, are gaining attention for their potential applications in biomedical, cosmetic, and food industries. Marine fungi, such as Asteromyces cruciatus, are particularly promising due to their ability to produce bioactive metabolites through the degradation of marine algal polysaccharides. This study investigates the metabolic diversity of A. cruciatus grown on different carbon sources: glucose, Durvillaea spp., and Macrocystis pyrifera. Crude extracts of fungal biomass were analyzed for total phenolic content (TPC), antioxidant capacity (TAC), toxicity, and phenolic compound identification using ultra-high-performance liquid chromatography coupled with high-resolution electrospray ionization mass spectrometry (UHPLC-MS/MS). The analysis revealed the presence of anthraquinone compounds, including emodin (0.36 ± 0.08 mg/g DW biomass) and citrereosein in glucose medium and citrereosein and endocrocin in M. pyrifera medium. No such compounds were detected in Durvillaea spp. medium. The glucose-grown extract exhibited the highest TPC (3.09 ± 0.04 mg GAE/g DW) and TAC (39.70 ± 1.0 µmol TEq/g biomass). Additionally, no detrimental effects were observed on a neuronal cell line. These findings highlight the influence of carbon sources on the production of bioactive metabolites and their functional properties, providing valuable insights into the biotechnological potential of A. cruciatus.

Discovery of Isograndidentatin D, a Novel Phenolic Glycoside, and Anti-Helicobacter pylori Phenolics from Salix koreensis Twigs.

Salix koreensis Anderss (Salicaceae), commonly referred to as Korean willow, is native to East Asia, particularly Korea and China, and it has been used in traditional Korean folk medicine for its potent anti-inflammatory, analgesic, and antioxidant properties. In our ongoing research efforts to discover biologically new natural products, phytochemical analysis on an ethanolic extract of S. koreensis twigs yielded the isolation and identification of ten phenolic compounds (1-10), including a newly discovered phenolic glycoside (1) named isograndidentatin D, isolated via HPLC purification. The structure of compound 1 was determined through extensive 1D and 2D NMR spectral data analysis and high-resolution electrospray ionization mass spectrometry (HR-ESIMS). Its absolute configuration was established using DP4+ probability analysis combined with gauge-including atomic orbital NMR chemical shift calculations and chemical reaction methods. The other known compounds were identified as isograndidentatin B (2), trichocarposide (3), glanduloidin C (4), tremuloidin (5), 3-O-acetylsalicin (6), 2-O-acetylsalicin (7), salicin (8), salireposide (9), and coumaric acid (10), confirmed by comparing their NMR spectra with previously reported data and further verified through liquid chromatography/mass spectrometry (LC/MS) analysis. The isolated compounds 1-10 were tested for their anti-Helicobacter pylori activities. Among these, compounds 4 and 5 demonstrated moderate anti-H. pylori activity at a concentration of 100 μM. Specifically, compound 5 showed an inhibitory activity of 35.9 ± 5.4%, making it slightly more potent than compound 4, with 34.0 ± 1.0% inhibition. These results were comparable to that of quercetin, a known anti-H. pylori agent used as a positive control in this study, which showed 38.4 ± 2.3% inhibition. The remaining compounds exhibited very weak inhibitory effects. This study highlights the potential of S. koreensis twigs as a valuable natural source of bioactive compounds for therapeutic applications against H. pylori.

Three new xanthones and other anti-inflammatory components from the aerial parts of Hypericum beanii.

Hypericum beanii, a traditional folk medicine plant, has been employed in treating various inflammation-related diseases. In this study, three new prenylated xanthones, named beanigenin A (1), beanigenin B (2), and beanigenin C (3), along with twenty-five known compounds (4-28), were isolated from the aerial parts of H. beanii. The new xanthones were elucidated based on modern spectroscopic experiments, including nuclear magnetic resonance spectroscopy (NMR) techniques, high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and electronic circular dichroism (ECD). All the compounds were evaluated for their anti-inflammatory effects by measuring their inhibitory effect on nitric oxide (NO) production in LPS-stimulated RAW 264.7 macrophages. Our findings showed that compounds 1-10, 12, 14, 21-23, 26, and 28 displayed significant anti-inflammatory effects, with IC50 values ranging from 0.82 to 9.71μM. The MOE software was utilized to conduct an in silico evaluation of the potential inhibitory activity of the three new xanthones against inducible NO synthase (iNOS) and cyclooxygenase 2 (COX-2) proteins. The results indicated that the three new xanthones demonstrated a high binding affinity with both iNOS and COX-2 proteins.

Brefeldin A-A Major Pathogenic Factor of Peanut Pod Rot from Fusarium neocosmosporiellum.

Fusarium neocosmosporiellum is the main pathogen of peanut pod rot in China. To investigate the type of F. neocosmosporiellum toxin and its pathogenic mechanism, a macrolide, brefeldin A, was isolated. The structure of the compound was identified by 1D and 2D nuclear magnetic resonance (NMR) and high-resolution electrospray ionization-mass spectrometry (HR-ESI-MS). At the same time, the content of the compound in healthy and diseased peanut capsules was detected, and its plant toxicity to radish, mung bean, rice, and peanut seed radicle elongation and pathogenicity to peanut pod rot were evaluated. The results showed that brefeldin A at 50 μg/mL could significantly inhibit the radicle elongation of rice seeds. Brefeldin A was detected only in pods with peanut rot. Injecting 2 mg/mL brefeldin A solution into peanut pods caused the severe decay of peanut pods at the R3R4 stage, which is consistent with the symptoms of peanut rot.

Pyrimidine Nucleosides, Benzoic Acid Derivative, and Bipyridine From the Marine-Derived Streptomyces Sp. DS52.

Fourteen new compounds were isolated from marine-derived Streptomyces sp. DS52, including 12 pyrimidine nucleosides (1-12), 1 benzoic acid derivative (13), and 1 dipyridine derivative (14). Additionally, 28 known compounds (15-42) were identified. The structures of all compounds were elucidated through extensive analysis of nuclear magnetic resonance spectroscopic and high-resolution electrospray ionization mass spectroscopy data. Electronic circular dichroism (ECD) calculations were employed to investigate the configurations of compounds 1, 2, and 4-13. Bioactivity evaluations of all of the compounds showed that compound 41 exhibited significant cytotoxicity against the HCT-116 and MDA-MB-231 human cancer cell lines with IC50 values of 0.73±0.06 and 1.11±0.06µM, respectively. Notably, compounds 6, 7, 9, 11, 15, 33-38, 41, and 42 exhibited cytotoxicity against HCT-116 human colon cancer cell lines and MDA-MB-231 human breast cancer cell lines, with IC50 values ranging from 0.73±0.06 to 17.44±0.53µM and from 1.11±0.06 to 18.51±3.07µM, respectively.

Curcumaones A-N, sesquiterpenes from the secondary rhizomes of Curcuma wenyujin.

Fourteen undescribed sesquiterpenes, named curcumaones A-N (1-14), as well as forty-four (15-58) known ones, were isolated from the secondary rhizomes of Curcuma wenyujin. The structures and absolute configurations of 1-14 were elucidated based on NMR spectroscopic analyses, high resolution electrospray ionization mass spectroscopy (HRESIMS) data and electronic circular dichroism (ECD) spectral analysis. Among these, five sesquiterpenes with the peroxide linkage (1-5) were obtained and the change of chemical shift between the α-C connecting the peroxide linkage and the oxygen atom has been discussed. In addition, all the isolated compounds were evaluated for their agonistic effect on farnesoid X receptors (FXR) situated with human embryonic kidney (HEK) 293T cells and the results showed that compounds 12 and 14 exhibited a significant agonistic effect dose-dependently at 20, 50 and 100μM, while 8, 32, 17 and 34 possessed moderate to weak agonistic effects.

Uniform Macromolecules: Performance of Common Analytic Instruments in Detecting Impurities

AbstractInspired by the highly defined structure of biomacromolecules, e.g. deoxyribonuleic acid (DNA) and proteins, the preparation and characterization of sequence‐defined and uniform macromolecules gained interest in polymer chemistry. With the development of various synthetic approaches, the challenge of analyzing and confirming the uniform structures emerged. Here, the investigation on the performance of common analytical instruments for the characterization of uniform macromolecules regarding impurities of ±1 in degree of oligomerization is presented. Thus, different mixtures containing oligomers differing in one repeating unit of oligo(ethylene glycol)s (OEG)s, oligo(phenylene ethynylene)s (OPE)s, and Passerini oligomers, respectively, are synthesized, and analyzed by proton nuclear magnetic resonance spectroscopy (1H NMR), size exclusion chromatography (SEC), and high‐resolution electrospray ionization mass spectrometry (HR‐ESI‐MS). These results demonstrate the indispensability of a careful characterization using more than one technique for determining uniformity. In particular, the obtained SEC results show that it is a powerful tool for purity determination of low molecular weight oligomers.