Drymariamides A-J, Antiadipogenic Cyclopeptides Incorporating Noncanonical Amino Acids from Drymaria cordata.

Herein, we report an extensive phytochemical study on the whole plant of Drymaria cordata, which led to the isolation of ten new orbitides, named drymariamides A-J (1-10). Compounds 2, 3, and 5 incorporate rare residues of noncanonical amino acids of kynurenine (Kyn) or 3a-hydroxypyrroloindoline (HPI). Their structures with absolute configurations were elucidated by a combination of spectroscopic analysis, advanced Marfey's method, X-ray diffraction, and electronic circular dichroism analysis. Compounds 1-10 exhibited antiadipogenic effects in 3T3-L1 adipocytes, and the most potent compound 7 showed an EC50 value of 1.17 ± 0.19 µM.

Dichapetalins from the Twigs of Dichapetalum longipetalum with Cytotoxic Activities.

Continued efforts to expand the structural diversity of dichapetalins and explore further the cytotoxic structure-activity relationships have led to the isolation of 17 undescribed analogues, dichapelonins A-Q (1-17), and three known compounds (18-20) from the twigs of Dichapetalum longipetalum. Compounds 1-17 comprise five compound classes as classified by varied C6-C2 conjugates at the A ring of the 13,30-cyclodammarane skeleton, and their structures were determined by spectroscopic data analysis, experimental electronic circular dichroism measurements, and X-ray crystallography. Biological tests revealed compounds 1-7 with a phenyl-butadiene appendage to be the most potent cytotoxic compound type of those evaluated.

Discovery of four modified classes of triterpenoids delineated a metabolic cascade: compound characterization and biomimetic synthesis.

Chemical studies on Dichapetalum gelonioides have afforded 18 highly modified complex triterpenoids belonging to four compound classes as defined by the newly adapted functional motifs associated with the A ring of the molecules. Their structures were determined by solid data acquired by diverse methods. The biosynthetic pathway for the four compound classes was rationalized via cascade modifications involving diverse chemical events. The subsequent biomimetic syntheses afforded all the desired products, including compounds 16 and 19 that were not obtained in our purification, which validated the proposed biosynthetic pathway. Besides, some compounds exhibited strong cytotoxic activities, especially 2 and 4 showed nanomolar potency against the NAMALWA tumor cell line, and a gross structure-activity relationship (SAR) of these compounds against the tested tumor cell lines was delineated.

Enhanced Dielectric Properties of a Poly(dimethyl siloxane) Bimodal Network Percolative Composite with MXene.

Excellent comprehensive dielectric properties (including dielectric constant and loss) are essential for electromechanical transducers. This work introduced a bimodal network composite with poly(dimethyl siloxane) (PDMS) and delaminated Ti3C2Tx sheets (d-Ti3C2Tx) modified with hyperbranched polysiloxane (HPSi) (referred to as HPSi-d-Ti3C2Tx). Before the final cross-linking, HPSi-d-Ti3C2Tx, trapped with short-chain PDMS (CS-PDMS) and long-chain PDMS (CL-PDMS), was pre-reacted, which formed a distinct bimodal network structure. d-Ti3C2Tx/PDMS and HPSi-d-Ti3C2Tx/PDMS composites with different filler loadings were prepared, and their percolation thresholds (fc) were 1.32 and 1.43 vol %, respectively The dielectric constant of 1.40 vol % HPSi-d-Ti3C2Tx/PDMS is 23.7 at 102 Hz, which is 1.5 times that of 1.28 vol % d-Ti3C2Tx/PDMS and 8.5 times that of pure PDMS. Meanwhile, the dielectric loss of HPSi-d-Ti3C2Tx/PDMS composite is still relatively small (0.11 at 103 Hz). The origin of dielectric property optimization of the composite is attributed to the boundary capacitor model, the accumulated charges at the interfaces between the conductive filler and the insulating polymer matrix of the composite, and the distinct bimodal network structure.

Suadimins A-C, Unprecedented Dimeric Quinoline Alkaloids with Antimycobacterial Activity from Melodinus suaveolens.

The suadimins A-C (1-3) from Melodinus suaveolens are the first example of monoterpenoid quinoline alkaloid dimers featuring an unprecedented carbon skeleton. Their structures and absolute configurations were established on the basis of extensive spectroscopic analyses, electric circular dichroism (ECD), and X-ray crystallography. Suadimin A showed significant antimycobacterial activity in vitro with an MIC90 of 6.76 µM against the H37Rv strain of M. tuberculosis.

Structural Elucidation and Bioinspired Total Syntheses of Ascorbylated Diterpenoid Hongkonoids A-D.

Hongkonoids A-D (1-4), the first example of ascorbylated terpenoids featuring a unique 5,5,5-fused tricyclic spiroketal butyrolactone moiety and diterpenoid-derived long chain, were isolated from Dysoxylum hongkongense. Their structures were unambiguously assigned by a combination of spectroscopic data, chemical degradation, X-ray crystallography, CD analysis, and total synthesis. The total syntheses of compounds 1-4 were effectively accomplished by a convergent strategy with the longest linear sequences of 12-14 steps and overall yields of 5.4-9.6%. Notably, we exploited a bioinspired one-pot method to construct the key intermediate 14 from an easily made compound 12 by involving the cascade reactions of an elaborate Claisen rearrangement, deprotections, and a 5-exo-trig cyclization. The desired major epimer 14a was then transformed to the main building block 21. Assembly of 21 and the long chain vinyl iodide 7 was made by an NHK coupling reaction to furnish the framework of 1-4. Some of the hongkonoids and/or synthetic analogs showed significant to moderate inhibitory activities against NF-κB, 11ß-HSD1, and sterol synthesis. The most active NF-κB inhibitor 34 exhibited distinct inhibition on the LPS-induced inflammatory responses in RAW 246.7 and primary BMDM cells.

Cascarinoids A-C, a Class of Diterpenoid Alkaloids with Unpredicted Conformations from Croton cascarilloides.

Cascarinoids A-C (1-3), a new class of diterpenoid alkaloids with unpredicted conformations, were isolated and structurally characterized from Croton cascarilloides. It was demonstrated that the dispersion interaction might be one of the main contributors that stabilized the folded conformations for compounds 1-3. Compounds 2 and 3 showed moderate immunosuppressive activity against T and/or B lymphocyte cells.

Complete genome sequence of Methylophilus sp. TWE2 isolated from methane oxidation enrichment culture of tap-water.

The non-methane-utilizing methylotroph, Methylophilus sp. TWE2, was isolated from tap-water during the enrichment of methanotrophs with methane. The complete genome sequence of strain TWE2 showed that this bacterium may convert methanol to formaldehyde via catalysis of methanol dehydrogenase (MDH), after which formaldehyde would be assimilated to biomass through the ribulose monophosphate (RuMP) pathway or dissimilated via the tetrahydromethanopterin (H4MPT) pathway. The deficiency of glycolysis and the TCA cycle indicate that strain TWE2 may be an obligate methylotroph. This is the first complete genome sequence of the genus Methylophilus.

Dectin-2 polymorphism associated with pulmonary cryptococcosis in HIV-uninfected Chinese patients.

Dectin-2 is a C-type lectin receptor that can recognize critical structures of fungi and involve in the host immune response after pulmonary fungal infections. We aimed to investigate the association between Dectin-2 genetic polymorphisms and cryptococcosis among a series of human immunodeficiency virus (HIV)-uninfected Chinese patients. In this case control study, a total of 251 patients with cryptococcosis and 464 healthy controls were included. One tag-single nucleotide polymorphism (SNP) (rs11045418) located at 5'-flanking region of Dectin-2 gene was selected and genotyped in this study. Among 251 patients, there were 108 (43%) meningitis patients including 73 (67.7%) healthy ones, 74 (29.5%) pulmonary infected patients including 49 (66.2%) healthy ones, and 69 (27.5%) patients with both neural and pulmonary infection including 38 (55.1%) immunocompetent ones. One hundred and forty-three (74 plus 69) patients with pulmonary cryptococcosis and 177 (108 plus 69) patients with cryptococcal meningitis were compared with controls, respectively. Three samples from 143 pulmonary infected patients failed in genotyping. There was a significant difference between 86 immunocompetent pulmonary infected patients and controls in the overdominant model (C/T vs. T/T + C/C; OR, 0.59; 95%CI, 0.37-0.94; P, .026). Similar but not significant difference was found between the overall pulmonary infected patients and the controls in the overdominant model (OR, 0.77; 95%CI, 0.52-1.12; P, .17). No such difference was found between controls and patients with cryptococcal meningitis. Our study firstly showed a genetic association between Dectin-2 and pulmonary cryptococcosis.

[Thermal treatment behavior of PCDD/Fs on the fly ash from medical waste incineration].

PCDD/Fs formation distribution in gas phase and solid phase of medical waste incineration fly ash under both the flowing nitrogen and static air condition were studied within temperature range of 200-450 degrees C. Under the flowing nitrogen, PCDD/Fs in solid phase increased with temperature increase, which reached the maximum concentration at 350 degrees C, both the TEQ and total concentration increased 46.0% and 26.0% respectively of original concentration, then, which decreased with temperature's rising, reaching the lowest level at 450 degrees C, of which 86.8% and 80.5% respectively in turn removed. Under the static air, the maximum concentration in solid phase occurred at 250 degrees C, both the TEQ and total concentration increased 20.7% and 28.7% respectively of original concentration, then, which decreased with temperature increase, reaching the lowest level at 450 degrees C, of which 99.5% and 99.5% respectively in turn removed. There were small generation of PCDD/Fs in gas phase, which took only 0.11%-2.16% of the total quantity of PCDD/Fs in both gas phase and solid phase. The optimal conditions for thermal treatment in this study were under the static air at temperature of 450 degrees C in duration of 1 h. The mechanism of destruction played the main role in the thermal treatment, while dechlorination and desorption acted as minor role in this study.