Application of Dearomatization Strategy on the Synthesis of Furoquinolinone and Angelicin Derivatives

The oxidative dearomatization of 3-(3-alkynyl-4-hydroxyphenyl)propanoic acid is combined with a cascade transition-metal catalyzed cyclization/addition/aromatization/lactamization sequence, which provides a novel approach to prepare furoquinolinone and angelicin derivatives in a convergent and efficient manner

Supplementary materials from Supply chain loss from easing COVID-19 restrictions: an evolutionary economic-epidemiological modelling study

Additional data analysis and visualizatio

Lack of Metabolic Activation and Predominant Formation of an Excreted Metabolite of Nontoxic Platynecine-Type Pyrrolizidine Alkaloids

Pyrrolizidine alkaloid (PA) poisoning is well-known because of the intake of PA-containing plant-derived natural products and PA-contaminated foodstuffs. Based on different structures of the necine bases, PAs are classified into three types: retronecine, otonecine, and platynecine type. The former two type PAs possessing an unsaturated necine base with a 1,2-double bond are hepatotoxic due to the P450-mediated metabolic activation to generate reactive pyrrolic ester, which interacts with cellular macromolecules leading to toxicity. With a saturated necine base, platynecine-type PAs are reported to be nontoxic and their nontoxicity was hypothesized to be due to the absence of metabolic activation; however, the metabolic pathway responsible for their nontoxic nature is largely unknown. In the present study, to prove the absence of metabolic activation in nontoxic platynecine-type PAs, hepatic metabolism of platyphylline (PLA), a representative platynecine-type PA, was investigated and directly compared with the representatives of two toxic types of PAs in parallel. By determining the pyrrolic ester-derived glutathione conjugate, our results confirmed that the major metabolic pathway of PLA did not lead to formation of the reactive pyrrolic ester. More interestingly, having a metabolic rate similar to that of toxic PAs, PLA also underwent oxidative metabolisms mediated by P450s, especially P450 3A4, the same enzyme that catalyzes metabolic activation of two toxic types of PAs. However, the predominant oxidative dehydrogenation pathway of PLA formed a novel metabolite, dehydro­platyphylline carboxylic acid, which was water-soluble, readily excreted, and could not interact with cellular macromolecules. In conclusion, our study confirmed that the saturated necine bases determine the absence of metabolic activation and thus govern the metabolic pathway responsible for the nontoxic nature of platynecine-type PAs

SUPPLEMENTARY_MATERIALS – Supplemental material for When People Co-occur With Good or Bad Events: Graded Effects of Relational Qualifiers on Evaluative Conditioning

<p>Supplemental material, SUPPLEMENTARY_MATERIALS for When People Co-occur With Good or Bad Events: Graded Effects of Relational Qualifiers on Evaluative Conditioning by Sean Hughes, Yang Ye, Pieter Van Dessel and Jan De Houwer in Personality and Social Psychology Bulletin</p

hughes_online_appendix – Supplemental material for When People Co-occur With Good or Bad Events: Graded Effects of Relational Qualifiers on Evaluative Conditioning

<p>Supplemental material, hughes_online_appendix for When People Co-occur With Good or Bad Events: Graded Effects of Relational Qualifiers on Evaluative Conditioning by Sean Hughes, Yang Ye, Pieter Van Dessel and Jan De Houwer in Personality and Social Psychology Bulletin</p

Dicarabrones A and B, a Pair of New Epimers Dimerized from Sesquiterpene Lactones via a [3 + 2] Cycloaddition from Carpesium abrotanoides

Dicarabrones A and B, a pair of epimers possessing a new skeleton featuring a cyclopentane ring connecting two sesquiterpene lactone units, were isolated from the whole plant of Carpesium abrotanoides L. Their full structures were established on the basis of spectroscopic data and were further confirmed by single-crystal X-ray crystallography. They were presumably biosynthesized from two sesquiterpenoid monomers through a [3 + 2] cycloaddition. Dicarabrones A and B showed moderate effects on HL-60 cells with IC₅₀ values of 9.1 and 8.2 μM, respectively

Template-Directed Synthesis of Flexible Porphyrin Nanocage and Nanorings via One-Step Olefin Metathesis

We describe the fabrication of a suite of flexible porphyrin cages and nanorings from a simple tetraalkene-derived zinc porphyrin monomer via a highly efficient template-directed strategy. The zinc porphyrin monomers were preorganized together by coordination with N atoms of multidentate ligands. Subsequent one-step olefin metathesis furnished a bisporphyrin cage, a triporphyrin nanoring, and a hexaporphyrin nanoring. In the case of the hexaporphyrin nanoring, 24 terminal olefins from six porphyrin monomers reacted with each other to form 12 new double bonds, delivering the final product. The triporphyrin and hexaporphyrin nanorings were further employed as hosts to encapsulate C₆₀ and C₇₀

Flexible Optical Waveguides in Heterocyclic Schiff Base Self-Assembled Hydrogen-Bonded Solvates

Flexible fluorescent crystalline materials exhibit both mechanical and optical properties and have received great attention due to their potential applications in flexible optical devices. Simultaneously adjusting the mechanical and optical properties of crystalline materials remains interesting and challenging. In the present work, a guest molecule was introduced via hydrogen-bonded solvation, which achieved excellent mechanical elasticity and higher fluorescence emission than that of the host heterocyclic Schiff base molecule crystal itself. The crystal structure–property relationship and the molecular mechanism of the elasticity were then investigated in detail. It revealed that solvent molecules play a key role in changing both the stacking of fluorescent molecules and the interaction energy framework. In addition, the flexible fluorescent solvate exhibits a good waveguide property. A bent crystal was found to have a larger optical loss coefficient than a straight crystal. Furthermore, the size effect on the optical loss coefficient of the waveguide was discussed in which the optical loss coefficient decreases as the sizes increase. Such a size effect is usually neglected in waveguide material research and should be complemented in the performance evaluation of optical waveguides

DataSheet_1_Causal associations of male infertility with stroke: a two-sample Mendelian randomization study.pdf

BackgroundStroke is a devastating global health issue, with high mortality and disability rates. The increasing prevalence of male infertility among reproductive-aged men has become a growing concern worldwide. However, the relationship between male infertility and stroke incidence remains uncertain. This study aimed to address this knowledge gap by employing a Mendelian randomization (MR) approach.MethodUtilizing genetic instrumental variables derived from a genome-wide association study (GWAS) on male infertility and stroke, a two-sample MR design was implemented. Five different analysis methods, with inverse-variance weighted as the primary approach, were used to examine the genetic causal associations between male infertility and various stroke subtypes. Heterogeneity analysis, pleiotropy tests, and leave-one-out validation were conducted to assess heterogeneity, evaluate pleiotropy, and ensure the robustness of the findings.ResultThe results indicate a potential lower risk of small vessel stroke associated with male infertility (odds ratio, 95% confidence interval: 0.82, 0.68 to 0.99, p=0.044), although no significant impact on other stroke subtypes was observed. The study exhibited low heterogeneity and no apparent pleiotropy; however, the stability of the results was not optimal.ConclusionMale infertility might potentially confer a protective effect against small vessel stroke risk. Caution is warranted due to potential confounding factors. Additional studies are necessary to confirm these findings and provide further validation.</p

Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor

We present the formation of a series of chiral metalla­cycles and metalla­cages by the use of a BINOL-derived dicarboxylate as a donor that is capable of affording a variety of coordination angles between its two Lewis basic sites. Two squares, two rhomboids, two tetragonal prisms, and one hexagonal prism were successfully formed when the chiral dicarboxylate donor self-assembled with one of four ditopic Pt­(II) complexes, including two bimetallic 180° Pt-based acceptors, a 120° bimetallic Pt-based acceptor, and a 90° mononuclear Pt-based acceptor. Their structures were well characterized by ³¹P­{¹H} NMR, ESI-MS, CD, and optical rotation analyses