Antitumor studies evaluation of triphenylphosphine ruthenium complexes with 5,7-dihalo-substituted-8-quinolinoline targeting mitophagy pathways.

Both ruthenium-containing complexes and 8-quinolinoline compounds have emerged as a potential novel agent for malignant tumor therapy. Here, three triphenylphosphine ruthenium complexes, [Ru(ZW1)(PPh3)2Cl2] (PPh3 = triphenylphosphine) (RuZ1), [Ru(ZW2)(PPh3)2Cl2] (RuZ2) and [Ru(ZW2)2(PPh3)Cl2]·CH2Cl2 (RuZ3) bearing 5,7-dichloro-8-quinolinol (H-ZW1) and 5,7-dichloro-8-hydroxyquinaldine (H-ZW2), have been synthesized, characterized and tested for their anticancer potential. We showed that triphenylphosphine ruthenium complexes RuZ1-RuZ3 impaired the cell viability of ovarian adenocarcinoma cisplatin-resistant SK-OV-3/DDP (SKO3CR) and SK-OV-3 (SKO3) cancer cells with greater selectivity and specificity than cisplatin. In addition, RuZ1-RuZ3 show higher excellent cytotoxicity than cisplatin towards SKO3CR cells, with IC50 values of 9.66 ± 1.08, 4.05 ± 0.67 and 7.18 ± 0.40 µM, respectively, in which the SKO3CR cells was the most sensitive to RuZ1-RuZ3. Depending on the substituent type, the antiproliferative ability of RuZ1-RuZ3 followed the trend: -CH3 > -H. However, RuZ1-RuZ3 have no obvious toxicity to normal cell HL-7702. Besides, RuZ1 and RuZ2 could induce mitophagy related-apoptosis pathways through suppression of mitochondrial membrane potential (ΔΨm), accumulation of [Ca2+] and reactive oxygen species (ROS), and regulation of LC3 II/LC3 I, Beclin-1, P62, FUNDC1, PINK1, Parkin, cleaved-caspase-3, caspase-9 and cytochrome c signaling pathway, and hindering the preparation of mitochondrial respiration complexes I and IV and ATP levels. Mechanistic study revealed that RuZ1 and RuZ2 induce apoptosis in SKO3CR cells via mitophagy related-apoptosis pathways induction and energy (ATP) generation disturbance. Taken together, the studied triphenylphosphine ruthenium complexes RuZ1-RuZ3 are promising chemotherapeutic agents with high effectiveness and low toxicity.

Stability studies of ALD-52 and its homologue 1P-LSD.

With the emergence of new psychoactive substances (NPSs) over the years, the substances detected on stamps (also known as blotter papers) have also evolved from the traditional drug-lysergic acid diethylamide (LSD) to the multiple variants of lysergamides such as ALD-52 and 1P-LSD. The analysis of such blotter papers is usually done by solvent extraction followed by identification using gas chromatography-mass spectrometry (GC-MS). This study has shown that hydrolysis to form LSD was observed in GC-MS analysis when ALD-52 was extracted with methanol. The extraction of ALD-52 using other solvents such as acetonitrile, ethanol, isopropyl alcohol, ethyl acetate, and acetone, followed by GC-MS analysis, was investigated. It is shown that alcoholic solvents such as methanol and ethanol will result in the conversion of ALD-52 to LSD during GC-MS analysis, whereas the sterically hindered isopropyl alcohol will prevent this conversion. Investigation also shows that the hydrolysis of ALD-52 to LSD occurs at the GC injector port. It was also observed that the degree of hydrolysis was more pronounced at a lower concentration (0.1 mg/mL). The study was extended to a close analog-1P-LSD, and the results showed that 1P-LSD similarly hydrolyzes to LSD. However, 1P-LSD was observed to be more stable than ALD-52 due to steric hindrance because of the propanoyl group.

Porous and Stable Zn-Series Metal-Organic Frameworks as Efficient Catalysts for Grafting Wood Nanofibers with Polycaprolactone via a Copolymerization Approach.

A hydrothermal method was used to synthesize two highly stable Zn(II) metal-organic frameworks (MOFs), namely, [Zn2(L)2(HIPA)]n (1) and [Zn9(L)6(BTEC)3(H2O)4·6H2O]n (2) (HL = 3-amino-1H-1,2,4-triazole, H2HIPA = 5-hydroxyisophthalic acid, H4BTEC = benzene-1,2,4,5-tetracarboxylic acid). The physicochemical properties of 1 and 2 were characterized using a range of analytical techniques. The scanning electron microscopy images confirmed the stability of the MOFs under heating at 120 °C for 12 h. Following their preparation, the two MOFs were used as catalysts in the grafting of poly(ε-caprolactone) on wood nanofibers (WNFs) by means of a homogeneous ring-opening polymerization protocol in an ionic liquid. The grafting ratio achieved using catalyst 1 was higher than that achieved for catalyst 2, wherein a maximum of 92.43% was obtained using the former. Under comparable reaction conditions, the grafting ratio of 1 was found to be significantly higher than those achieved using 4-dimethylamino pyridine, Sn(Oct)2, and UiO-67 catalysts. In addition, fluorescence emission was detected from the residual catalysts present in the products. The calculated electrostatic potentials and average local ionization energies indicated that the grafting of ε-caprolactone on the WNFs follows a "coordination-insertion" mechanism. Overall, these two new and efficient MOF catalysts have the potential to replace highly toxic traditional catalysts in polymerization reactions. The grafted cellulose material with fluorescence emission may also be suitable for use in biomedical applications.

Retraction Notice to: miR-363 Alleviates Detrusor Fibrosis via the TGF-ß1/Smad Signaling Pathway by Targeting Col1a2 in Rat Models of STZ-Induced T2DM.

[This retracts the article DOI: 10.1016/j.omtn.2020.07.001.].

Novel zinc(II)-curcumin molecular probes bearing berberine and jatrorrhizine derivatives as potential mitochondria-targeting anti-neoplastic drugs.

Berberine and jatrorrhizine are major bioactive components that are emerging as potential anti-cancer drugs. However, no zinc(II) - berberine/jatrorrhizine - curcumin compounds have been reported in the literature to date. Therefore, the molecular mechanisms associated with their cytotoxicity remain unexplored. To investigate the potential mitochondria-targeting ability, anti-neoplastic activity, and utility in cell imaging of berberine and jatrorrhizine derivates, four novel zinc(II) complexes, [Zn(Ber)(H2O)Cl2] (Zn(Ber)), [Zn(Ber)(Cur)Cl] (Zn(CurBer)), [Zn(Jat)(H2O)Cl2] (Zn(Jat)), and [Zn(Jat)(Cur)Cl] (Zn(CurJat)) bearing the berberine-derived ligand 2,2,2-trifluoroacetate 10-methoxy-9-((9-((2-(pyridin-2-yl)ethyl)amino)nonyl)oxy) -5,6-dihydro- [1,3]dioxolo[4,5-g]isoquinolino [(Torre et al., 2015; de Ruijter et al., 2020) 3,23,2-a]isoquinolin-7-ium (Ber), the jatrorrhizine-derived ligand 2,2,2-trifluoroacetate 2,9,10-trimethoxy-3-((9- ((2-(pyridin-2-yl)ethyl)amino)nonyl)oxy)-5,6-dihydroisoquinolino [(Torre et al., 2015; de Ruijter et al., 2020) 3,23,2-a]isoquinolin-7-ium (Jat), and/or curcumin (H-Cur) were first synthesised in this study. Zn(Ber), Zn(CurBer), Zn(Jat), and Zn(CurJat) showed higher cytotoxicity against human MCF-7 (breast adenocarcinoma) cells than did cisplatin, with IC50 values ranging from 0.21 to 4.45 µM. The anti-neoplastic activities of the zinc(II) - berberine/jatrorrhizine - curcumin complexes were in the following order: Zn(CurBer) > Zn(CurJat) > Zn(Ber) > Zn(Jat) > cisplatin > H-Cur > Ber > Jat > ZnCl2. Among these, Zn(CurBer) displayed the highest cytotoxicity (0.21 ± 0.06 µM). Furthermore, mechanistic investigations revealed that Zn(CurBer) and Zn(CurJat) could accumulate in the mitochondria, exhibit red fluorescence, and trigger mitophagy and apoptosis. In vivo anti-cancer evaluations also suggested that Zn(CurBer) inhibited MCF-7 xenograft tumour growth more effectively than cisplatin and Zn(CurJat). This is the first report describing the synthesis of zinc(II) - berberine/jatrorrhizine - curcumin complexes and their potential use as molecular probes and mitochondria-targeting anti-neoplastic drugs.

Eleven-Residue Peptaibols Isolated from Trichoderma longibrachiatum Rifai DMG-3-1-1and Their Structure-Activity Relationship.

Total 23 eleven-residue peptaibols, including five reported ones (1-5) in our previous work, were isolated from the fungus Trichoderma longibrachiatum Rifai DMG-3-1-1, which was obtained from the mushroom Clitocybe nebularis (Batsch) P. Kumm. The structures of the 13 new peptaibols (6-10 and 12-19) were determined by their NMR and MALDI-MS/MS data, their absolute structures were further determined by Marfey's analyses and their ECD data. Careful comparison of the structures of 1-23 showed that only seven residues varied including the 2nd (Gln2 /Asn2 ), 3rd (Ile3 /Val3 ), 4th (Ile4 /Val4 ), 6th (Pro6 /Hyp6 ), 8th (Leu8 /Val8 ), 10th (Pro10 /Hyp10 ) and 11th (Leuol11 /Ileol11 /Valol11 ) residues. Comparison of the IC50 s against the three tested cell lines of 1-23 indicated that 2nd, 3rd and 4th amino acid residues affected their cytotoxicities powerfully. Compounds 2, 5, 9, 11, 21 and 22 showed moderate antibacterial activities against Staphylococcus aureus MRSA T144, which also showed stronger cytotoxicities against BV2 and MCF-7 cells.

Cell nucleus localization and high anticancer activity of quinoline-benzopyran rhodium(III) metal complexes as therapeutic and fluorescence imaging agents.

Four novel rhodium(III) complexes, [RhIII(QB1)Cl3(DMSO)] (RhN1), [RhIII(QB2)Cl3(CH3OH)]·CH3OH (RhN2), [RhIII(QB3)Cl3(CH3OH)]·CH3OH (RhS), and [RhIII(QB4)Cl3(DMSO)] (RhQ), bearing quinoline-benzopyran ligands (QB1-QB4) were synthesized and used to develop highly anticancer therapeutic and fluorescence imaging agents. Compared with the QB1-QB4 ligands (IC50 > 89.2 ± 1.7 µM for A549/DDP), RhN1, RhN2, RhS and RhQ exhibit selective cytotoxicity against lung carcinoma cisplatin-resistant A549/DDP (A549CDDP) cancer cells, with IC50 values in the range of 0.08-2.7 µM. The fluorescent imaging agent RhQ with the more extended planar QB4 ligand exhibited high anticancer activity in A549CDDP cells and was found in the cell nucleus fraction, whereas RhS had no fluorescence properties. RhQ and RhS may trigger cell apoptosis by causing DNA damage and initiating the mitochondrial dysfunction pathway. Furthermore, RhQ has a higher antitumor efficacy (ca. 55.3%) than RhS (46.4%) and cisplatin (CDDP, 33.1%), and RhQ demonstrated significantly lower toxicity in vivo than CDDP, making it a promising Rh(III)-based anticancer therapeutic and fluorescence imaging agent.

Novel bifluorescent Zn(II)-cryptolepine-cyclen complexes trigger apoptosis induced by nuclear and mitochondrial DNA damage in cisplatin-resistant lung tumor cells.

Four novel bifluorescent Zn(II)-cryptolepine-cyclen complexes, namely [Zn(BQTC)]Cl2 (Zn(BQTC)), [Zn(BQA) (Cur)Cl] (Zn(BQACur)), [Zn (TC)]Cl2 (Zn(TC)), and [Zn (AP) (Cur)Cl] (Zn(APCur)), bearing curcumin (H-Cur), cyclen (TC), 1,10-phenanthrolin-5-amine (AP), and novel cryptolepine-cyclen derivatives (BQTC and BQA) were prepared for cell nucleus- and mitochondria-specific imaging. MTT assay results indicated that Zn(BQTC) and Zn(BQACur) exhibit stronger anticancer activity against cisplatin-resistant A549R lung tumor cells than ZnCl2, Zn(TC), Zn(APCur), H-Cur, TC, AP, BQTC, and BQA. Due to the dual fluorescence characteristic of Zn(BQTC), selective fluorescence imaging of the nucleus and mitochondria of A549R cancer cells was conducted. Further, Zn(BQTC), obtained by the functionalization of Zn(TC) with cryptolepine derivative substituents, efficiently inhibited DNA synthesis, thus resulting in high cytotoxicity (selective for A549R lung tumor cells) accompanied by DNA impairment in nuclear and mitochondrial fractions. Additionally, Zn(BQTC) caused severe damage to the mitochondrial DNA (mtDNA) and nuclear DNA (nDNA), sequentially disrupted mitochondrial and nuclear functions, and promoted the DNA damage-induced apoptotic signaling pathway and adenosine triphosphate depletion (ATP). Thus, Zn(BQTC) can be used as an anticancer drug by targeting mtDNA and nDNA. Most importantly, Zn(BQTC) showed higher efficacy in inhibiting cancer growth (55.9%) in A549R tumor-bearing mice than Zn(TC) (31.2%) and cisplatin, along with a promising in vivo safety profile. These results demonstrate the applicability of the developed novel bifluorescent Zn(II)-cryptolepine-cyclen complexes as promising DNA-targeting anticancer agents for cancer treatment.

Longibrachiamide A, a 20-Residue Peptaibol Isolated from Trichoderma longibrachiatum Rifai DMG-3-1-1.

Longibrachiamide A (1), a new 20-residue peptaibol, along with three known ones (2-4), were isolated from the fungus Trichoderma longibrachiatum Rifai DMG-3-1-1, isolated from a mushroom Clitocybe nebularis (Batsch) P. Kumm, which was collected from coniferous forest of northeast China in our previous work. The structure of longibrachiamide A (1) was determined by its NMR and ESI-MS/MS data, the absolute configuration of 1 was further determined by Marfey's analyses. And the complete NMR data of 2-4 were also reported for the first time. The similar CD spectra of 1-4 showed that they all had mixed 310 -/α-helical conformations. Compounds 1-4 showed strong cytotoxicities against BV2, A549 and MCF-7 cells, and also showed moderate inhibitory effects against the tested Gram-positive bacteria, including MRSA T144 and VRE-10.

A new class of nickel(II) oxyquinoline-bipyridine complexes as potent anticancer agents induces apoptosis and autophagy in A549/DDP tumor cells through mitophagy pathways.

A new class of nickel(II) oxyquinoline-bipyridine complexes, namely, [Ni(La1)2(Lb6)] (Ni1), [Ni(La1)2(Lb2)] ·CH3OH (Ni2), [Ni(La7)2(Lb11)]·2H2O (Ni3), [Ni(La1)2(Lb9)] (Ni4), [Ni(La1)2(Lb8)] (Ni5), [Ni(La2)2(Lb1)] (Ni6), [Ni(La2)2(Lb6)]·CH3OH (Ni7), [Ni(La2)2(Lb11)]·CH3OH (Ni8), [Ni(La2)2(Lb3)] (Ni9), [Ni(La2)2(Lb2)]·CH3OH (Ni10), [Ni(La2)2(Lb5)]·CH3OH (Ni11), [Ni(La2)2(Lb7)] (Ni12), [Ni(La3)2(Lb2)] (Ni13), [Ni(La4)2(Lb4)]·2CH3OH (Ni14), [Ni(La4)2(Lb8)]·2.5CH3OH (Ni15), [Ni(La4)2(Lb11)]·1.5CH3OH (Ni16), [Ni(La5)2(Lb7)] (Ni17), [Ni(La5)2(Lb10)]·CH3OH (Ni18), [Ni(La6)2(Lb11)]·3CH3OH (Ni19), [Ni(La7)2(Lb7)]·2CH3OH (Ni20), [Ni(La7)2(Lb8)]·2CH3OH (Ni21) and [Ni(La7)2(Lb1)]·2CH3OH (Ni22) bearing oxyquinoline (H-La1-H-La7) and bipyridine derivatives (Lb1-Lb11) were synthesized and characterized by elemental analysis, X-ray crystallography, infrared (IR) spectroscopy and electrospray mass spectrometry (ESI-MS). An MTT method suggested that the IC50 values of Ni1-Ni22 for A549/DDP tumor cells were 0.25-25.14 µM, but these complexes exhibited low cytotoxicity toward normal HL-7702 cells (>50 µM). Ni2 could induce A549/DDP tumor cell apoptosis, cause a decrease in the mitochondrial membrane potential (MMP, ΔΨm), and increase the intracellular [Ca2+] and reactive oxygen species (ROS) levels better than Ni10, Ni13, and Ni14. Autophagic and western blot assays showed that Ni2, Ni10, Ni13, and Ni14 could induce autophagy and regulate the expression of LC3 II/I, Beclin1, P62, PINK1, and Parkin proteins, and the inducibility activities were in the order of Ni2 > Ni14 > Ni13 > Ni10. Taken together, these results revealed that the nickel(II) oxyquinoline-bipyridine complex Ni2 inhibited cell growth in A549/DDP tumor cells via mitophagy pathways.

[Meta-analysis of efficacy and safety of Suhuang Zhike Capsules in treatment of chronic obstructive pulmonary disease].

This study aims to evaluate the effectiveness and safety of Suhuang Zhike Capsules in treating chronic obstructive pulmonary disease. The Chinese and English databases were searched(from the establishment to July 2021) for randomized controlled trials(RCTs) on the treatment of chronic obstructive pulmonary disease with Suhuang Zhike Capsules, yielding 130 articles and finally 12 eligible RCTs. The 12 RCTs enrolled a total of 1 159 patients(579 in experimental group, 580 in control group), with 728 males(62.8%) and 431 females(37.2%). Meta-analysis showed that the conventional western medicine combined with Suhuang Zhike Capsules increased clinical efficacy(OR=4.31, 95%CI[2.88, 6.46], Z=7.08, P<0.000 01), forced expiratory volume in one second(FEV1)(SMD=0.88, 95%CI[0.60, 1.16], Z=6.24, P<0.000 01), forced vital capacity(FVC)(SMD=0.96, 95%CI[0.38, 1.55], Z=3.22, P=0.001), forced vital capacity rate of one second(FEV1/FVC%)(SMD=0.85, 95%CI[0.51, 1.19], Z=4.92, P<0.000 01), and maximum voluntary ventilation(MVV)(SMD=0.61, 95%CI[0.39, 0.83], Z=5.40, P<0.000 01) compared with the conventional western medicine alone. The differences in residual volume/total lung capacity(RV/TLC)(SMD=-0.93, 95%CI[-3.38, 1.53], Z=0.74, P=0.46) and adverse reactions(OR=1.39, 95%CI[0.76, 2.56], Z=1.07, P=0.28) are insignificant. The study showed that the conventional western medicine combined with Suhuang Zhike Capsules could improve clinical efficacy and lung functions in the treatment of chronic obstructive pulmonary disease. In addition, the combination had been verified to be safe. However, in view of the uneven method quality, small sample size, and inconsistent outcome indicators of the included studies, higher-quality, multi-center, and large-sample RCTs are needed for further verification.

Complexes of Zn(II) with a mixed tryptanthrin derivative and curcumin chelating ligands as new promising anticancer agents.

In this study, two novel curcumin (H-Cur)-tryptanthrin metal compounds-[Zn(TA)Cl2], i.e., Zn(TA), and [Zn(TA)(Cur)]Cl, i.e., Zn(TAC)-were synthesized and investigated using 5-(bis-pyridin-2-ylmethyl-amino)-pentanoic acid (6,12-dioxo-6,12-dihydro-indolo[2,1-b]quinazolin-8-yl)-amide (TA) and H-Cur as the targeting and high-activity anticancer chemotherapeutic moieties, respectively. They were then compared with the di-(2-picolyl)amine (PA) Zn(II) complex [Zn(PA)Cl2], i.e., Zn(PA). When compared with Zn(PA) and cisplatin, the IC50 values of Zn(TA) and Zn(TAC) indicated that the compounds had high cytotoxicity against A549/DDP cancer cells, implying that the H-Cur-tryptanthrin Zn(II) compounds have the potential for use as anticancer drugs. We propose the use of synthesized theragnostic H-Cur-tryptanthrin Zn(II) complexes with nuclear-targeting and DNA-damaging capabilities as a simple therapeutic strategy against tumors. The Zn(TA) and Zn(TAC) complexes could be traced via red fluorescence and were found to accumulate in the cell nuclei and induce DNA damage, cell cycle arrest, mitochondrial dysfunction, and cell apoptosis both in vitro and in vivo. In addition, Zn(TAC) exhibited a higher antiproliferative effect on A549/DDP than Zn(TA) and Zn(PA), which was undoubtedly associated with the key roles of the novel tryptanthrin derivative TA and H-Cur in the Zn(TAC) complex.

Proteomic analysis reveals the molecular mechanism underlying the cold acclimation and freezing tolerance of wheat (Triticum aestivum L.).

Cold acclimation (CA) is an important evolutionary adaptive mechanism for wheat freezing resistence. To clarify the molecular basis of wheat CA and freezing tolerance, the effects of CA (4 °C) and non-CA (20 °C) treatments and freezing stress (-5 °C) on the proteins in the wheat crown were characterized via an iTRAQ-based proteomic analysis. A total of 669 differentially accumulated proteins (DAPs) were identified after the CA, of which seven were also DAPs in the CA plants exposed to freezing stress. Additionally, the 15 DAPs in the CA group and the 23 DAPs in the non-CA group after the freezing treatment differed substantially. Functional analyses indicated that CA enhanced freezing tolerance by regulating proteins involved in signal transduction, carbohydrate metabolism, stress and defense responses, and phenylpropanoid biosynthesis. An integrated transcriptomic, proteomic, and metabolomic analysis revealed significant changes in various components of the glutathione metabolic pathway. The overexpression and silencing of Wdhn13 in Arabidopsis and wheat resulted in increased tolerance and sensitivity to freezing stress, respectively, suggesting Wdhn13 promotes freezing tolerance. Overall, our study offers insights into the regulatory network underlying the CA and freezing tolerance of wheat, which may be useful for elucidating wheat freezing resistance.

Discovery of thirteen cobalt(II) and copper(II) salicylaldehyde Schiff base complexes that induce apoptosis and autophagy in human lung adenocarcinoma A549/DDP cells and that can overcome cisplatin resistance in vitro and in vivo.

In this study, 13 transition metal complexes, namely, [Cu(L1H)(H2O)2]·(H2O)·NO3 (1), [Cu(LnH2)2]·(NO3)·(H2O)2 (2, n = 2; 3, n = 3; 4, n = 4; 5, n = 5), [Co(LnH)2]2·(H2O)0.5 (6, n = 2; 7, n = 3; 8, n = 4; 9, n = 5), [Cu(L6H)0.5(L10H)0.5(phen)]·(CH3OH)0.25 (10), [Cu(L11H) (phen)]4·(H2O)9 (11), [Cu(L8H)0.27(L12H)0.73(phen)]4·(H2O)5.5(CH3OH) (12), and [Cu(L9H) (phen)]3·(H2O)7·(CH3OH) (13), were synthesized using Schiff base ligands and characterized by elemental analysis (EA), infrared spectroscopy (IR), and single-crystal X-ray diffraction (SC-XRD). Compared with complexes 1-9, complexes 10-13 displayed stronger cytotoxic activities against the tested A549/DDP cancer cells (IC50 = 0.97-3.31 µM), with differences greater than one order of magnitude. Moreover, complexes 11 and 13 could induce apoptosis and autophagy in A549/DDP cells via the mitochondrial dysfunction pathway that affects the regulation of autophagy- and mitochondrial-related proteins. Importantly, the results indicate that the two novel salicylaldehyde Schiff base analogs, 11 and 13, exhibited pronounced and selective activity against A549/DDP xenografts in vivo.

Syntheses, crystal structures and Hirshfeld surface analysis of (Z)-3-[(3-acetyl-2-hydroxyphenyl)amino]-2-bromoprop-2-enal and a novel ZnII complex.

A novel zero-dimensional dinuclear zinc complex, di-µ-acetato-1:2κ4O:O'-(µ-2-acetyl-6-{[(Z)-2-bromo-3-oxoprop-1-en-1-yl]azanidyl}phenolato-1κ2O1,O2:2κ3O1,N,O6)(N,N-dimethylacetamide-1κO)dizinc(II), [Zn2(C11H8BrNO3)(CH3COO)2(C4H9NO)] or [Zn2(L)(CH3COO)2(DMA)], 1, was synthesized using (Z)-3-[(3-acetyl-2-hydroxyphenyl)amino]-2-bromoprop-2-enal (H2L), which was synthesized from 1-(3-amino-2-hydroxyphenyl)ethanone and 2-bromomalonaldehyde. H2L and 1 were characterized by single-crystal X-ray diffraction, FT-IR spectroscopy and elemental analysis. Theoretical calculations of the bond orders and excited state of H2L confirmed that there is extensive electron delocalization in the H2L molecules. Single-crystal X-ray diffraction shows that the two Zn atoms are pentacoordinated in distorted trigonal bipyramidal configurations in the crystals of 1. The thermogravimetric analysis of 1 shows that the main frame of the complex remains stable to about 190 °C. Powder X-ray diffraction (PXRD) analysis shows that 1 possesses high purity and acid and alkali resistance. The intermolecular interactions of H2L and 1 were analyzed using Hirshfeld surface analysis and the results indicate that the H...H and O...H interactions of H2L and 1 play a considerable role in stabilizing the self-assembly process.

Chrysomutanin and related meroterpenoids from a DES mutant of the marine-derived fungus Penicillium chrysogenum S-3-25.

A new meroterpene, chrysomutanin (1), two new meroterpenoids (4 and 5) together with nine known ones were isolated from the diethyl sulphate (DES) mutant 3d10-01 of the marine-derived fungus Penicillium chrysogenum S-3-25. The structures of the isolated compounds were determined by their spectroscopic data, and the absolute configuration of 1 was determined by Rh2-induced electrical circular dichroism (ECD) analysis or by comparison of the measured ECD with that of the known compounds. The cytotoxic activity was preliminarily evaluated against five human cancer cell lines. HPLC-UV analysis showed that compounds 1-12 were all newly produced by the mutant, and were not detected from the initial strain S-3-25. Chrysomutanin (1) is a new member with a chain sesquiterpene unit to the family of meroterpenes. Present results confirm that DES mutagenesis strategy is an effective method to exploit the dormant metabolites of fungi.

Surfactin isoforms isolated from a mushroom derived Bacillus halotolerans DMG-7-2.

A new iso-C14 [Val2, Val7] surfactin isoform (1) together with eight known ones (2-9), was isolated from the culture of a mushroom derived bacterium, Bacillus halotolerans DMG-7-2. The structures of them were mainly elucidated by NMR and MS data, and the NMR data of 5 also was reported for the first time. The absolute configuration of 1 was determined by Marfey's analysis (for amino acid residues) and the 13C NMR calculation of the two plausible epimers of 1 (for fatty acid). Compounds 1-9 showed moderate cytotoxicity against two human cancer cell lines (A549, MCF-7) and mice microglial BV2 cells, the IC50 values ranged from 8.91 to 33.00 µM, and the IC50 values of the positive control 5-FU were 99.94, 71.49 and 0.12 µM, respectively.[Formula: see text].

Longibramides A-E, Peptaibols Isolated from a Mushroom Derived Fungus Trichoderma longibrachiatum Rifai DMG-3-1-1.

Five new peptaibols, longibramides A-E (1-5) with 11 amino acid residues, were isolated from a fungus Trichoderma longibrachiatum Rifai DMG-3-1-1, which was isolated from a mushroom Clitocybe nebularis (Batsch) P. Kumm collected from coniferous forest in the subboreal area of northeast China. The structures of longibramides A-E were determined by their spectroscopic data (NMR and MS-MS spectra), their absolute configurations were determined by X-ray diffractions and Marfey's analyses. The X-ray diffractions of longibramides A, B, and the similar CD spectra of A-E showed that they all had α-helix conformations. Longibramides B and E showed moderate cytotoxicities against BV2 and MCF-7 cells and also showed some inhibitory effects against methicillin-resistant Staphylococcus aureus MRSA T144. L-trans-Hyp was not commonly found in natural peptaibols, which was the 6th or 10th amino acid residue in longibramides C-E. The X-ray diffractions of longibramides A and B afforded the accuracy conformations of their secondary structures, which maybe help to interpret the structure-activity relationships of the family of peptaibols in the future.