Electrochemically Enabled Hydroxyphosphorylation of 1,3-Enynes to Access Phosphinyl-Substituted Propargyl Alcohols.

Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms of 1,3-enynes, despite of the various catalytic methods developed for hydrophosphorylation, the radical-mediated hetero-functionalization of two different atoms has been less explored. In this study, we disclosed an electrochemically induced hydroxyphosphorylation of 1,3-enynes for the construction of phosphinyl-substituted propargyl alcohols. The system involves the direct activation of both arylphosphine oxides and oxygen in ambient air with no external metal or additive needed. The use of electrochemistry ensures the regioselective, atom-economic and eco-friendly for the difunctionalization process. This strategy highlights the advantages of mild reaction conditions, readily available starting materials and broad substrate scope, showing its practical synthetic value in organic synthesis.

Screening high-risk population of persistent postpartum hypertension in women with preeclampsia using latent class cluster analysis.

BACKGROUND: A significant proportion of women with preeclampsia (PE) exhibit persistent postpartum hypertension (PHTN) at 3 months postpartum associated with cardiovascular morbidity. This study aimed to screen patients with PE to identify the high-risk population with persistent PHTN. METHODS: This retrospective cohort study enrolled 1,000 PE patients with complete parturient and postpartum blood pressure (BP) profiles at 3 months postpartum. The enrolled patients exhibited new-onset hypertension after 20 weeks of pregnancy, while those with PE superimposed upon chronic hypertension were excluded. Latent class cluster analysis (LCCA), a method of unsupervised learning in machine learning, was performed to ascertain maternal exposure clusters from eight variables and 35 subordinate risk factors. Logistic regression was applied to calculate odds ratios (OR) indicating the association between clusters and PHTN. RESULTS: The 1,000 participants were classified into three exposure clusters (subpopulations with similar characteristics) according to persistent PHTN development: high-risk cluster (31.2%), medium-risk cluster (36.8%), and low-risk cluster (32.0%). Among the 1,000 PE patients, a total of 134 (13.4%) were diagnosed with persistent PHTN, while the percentages of persistent PHTN were24.68%, 10.05%, and 6.25% in the high-, medium-, and low-risk clusters, respectively. Persistent PHTN in the high-risk cluster was nearly five times higher (OR, 4.915; 95% confidence interval (CI), 2.92-8.27) and three times (OR, 2.931; 95% CI, 1.91-4.49) than in the low- and medium-risk clusters, respectively. Persistent PHTN did not differ between the medium- and low-risk clusters. Subjects in the high-risk cluster were older and showed higher BP, poorer prenatal organ function, more adverse pregnancy events, and greater medication requirement than the other two groups. CONCLUSION: Patients with PE can be classified into high-, medium-, and low-risk clusters according to persistent PHTN severity; each cluster has cognizable clinical features. This study's findings stress the importance of controlling persistent PHTN to prevent future cardiovascular disease.

Evidence for the Involvement of Auxin, Ethylene and ROS Signaling During Primary Root Inhibition of Arabidopsis by the Allelochemical Benzoic Acid.

Allelopathy is mediated by plant-derived secondary metabolites (allelochemicals) which are released by donor plants and affect the growth and development of receptor plants. The plant root is the first organ which senses soil allelochemicals this results in the production of a shorter primary root. However, the mechanisms underlying this process remain elusive. Here, we report that a model allelochemical benzoic acid (BA) inhibited primary root elongation of Arabidopsis seedlings by reducing the sizes of both the meristem and elongation zones, and that auxin signaling affected this process. An increase in auxin level in the root tips was associated with increased expression of auxin biosynthesis genes and auxin polar transporter AUX1 and PIN2 genes under BA stress. Mutant analyses demonstrated that AUX1 and PIN2 rather than PIN1 were required for the inhibition of primary root elongation during BA exposure. Furthermore, BA stimulated ethylene evolution, whereas blocking BA-induced ethylene signaling with an ethylene biosynthesis inhibitor (Co2+), an ethylene perception antagonist (1-methylcyclopropene) or ethylene signaling mutant lines etr1-3 and ein3eil1 compromised BA-mediated inhibition of root elongation and up-regulation of auxin biosynthesis-related genes together with AUX1 and PIN2, indicating that ethylene signal was involved in auxin-mediated inhibition of primary root elongation during BA stress. Further analysis revealed that the BA-induced reactive oxygen species (ROS) burst contributed to BA-mediated root growth inhibition without affecting auxin and ethylene signals. Taken together, our results reveal that the allelochemical BA inhibits root elongation by increasing auxin accumulation via stimulation of auxin biosynthesis and AUX1/PIN2-mediated auxin transport via stimulation of ethylene production and an auxin/ethylene-independent ROS burst.

[Correlation between growth rate of corpus callosum and neuromotor development in preterm infants].

OBJECTIVE: To investigate the growth rate of corpus callosum by cranial ultrasound in very low birth weight preterm infants and to provide a reference for early evaluation and improvement of brain development. METHODS: A total of 120 preterm infants under 33 weeks' gestation were recruited and divided into 26-29(+6) weeks group (n=64) and 30-32(+6) weeks group (n=56) according to the gestational age. The growth rate of corpus callosum was compared between the two groups. The correlation between the corpus callosum length and the cerebellar vermis length and the relationship of the growth rate of corpus callosum with clinical factors and the neuromotor development were analyzed. RESULTS: The growth rate of corpus callosum in preterm infants declined since 2 weeks after birth. Compared with the 30-32(+6) weeks group, the 26-29(+6) weeks group had a significantly lower growth rate of corpus callosum at 3-4 weeks after birth, at 5-6 weeks after birth, and from 7 weeks after birth to 40 weeks of corrected gestational age. There was a positive linear correlation between the corpus callosum length and the cerebellar vermis length. Small-for-gestational age infants had a low growth rate of corpus callosum at 2 weeks after birth. The 12 preterm infants with severe abnormal intellectual development had a lower growth rate of corpus callosum compared with the 108 preterm infants with non-severe abnormal intellectual development at 3-6 weeks after birth. The 5 preterm infants with severe abnormal motor development had a significantly lower growth rate of corpus callosum compared with the 115 preterm infants with non-severe abnormal motor development at 3-6 weeks after birth. CONCLUSIONS: The decline of growth rate of corpus callosum in preterm infants at 2-6 weeks after birth can increase the risk of severe abnormal neuromotor development.

Access Polyarylbipyrazoles via Palladium-Catalysis and Visible-Light-Driven C(sp3)-P(V) Cleavage Relay Strategy.

An unprecedented palladium-catalyzed and visible-light-driven relay reaction of allenylphosphine oxide with in situ generated nitrile imines is presented for the direct synthesis of highly valuable polyarylbipyrazole skeletons. This one-pot strategy involves double 1,3-dipolar cycloaddition and C(sp3)-P(V) bond cleavage under photocatalyst-free and mild reaction conditions. The approach features simple operation, a high step economy, and a broad substrate scope, affording the corresponding products in moderate to excellent yields.

Pd-catalyzed divergent regioselective annulation of phosphinyl allenes accessing polyarylfurans and 2H-chromenes.

A novel and efficient regioselective annulation of phosphinyl allenes with 2-bromophenol or 1-bromo-2-naphthol is achieved by palladium catalysis. The divergent pathway delivers structurally diverse polyarylfurans and 2H-chromene skeletons via two different Heck-type annulations. This protocol represents regioselectivity-tunable transformation of allenes into functionalized O-containing heterocycles with excellent group compatibility.

"Boomerang" Strategy in Carbohydrate Chemistry: Diastereoselective Synthesis of C-Glycosylated Benzothiazoles from ortho-Isocyanophenyl Thioglycosides.

This paper reveals a novel "boomerang" strategy in the expedient and diastereoselective synthesis of C-nucleoside analogues. Bench-stable ortho-isocyanophenyl thioglycosides can be converted to glycosyl radicals through rapid and efficient C-S bond homolysis when they are irradiated by visible light. The glycosyl radicals are subsequently trapped by the corresponding leaving group or other radical acceptors to provide diverse C-nucleoside analogues under mild conditions.

Regulation of the class II and class I MHC pathways in human THP-1 monocytic cells by interleukin-27.

Interleukin-27 (IL-27) is an IL-12-related cytokine that can promote both anti- and pro-inflammatory immune responses. In this study, we used the promonocytic cell line THP-1, an established model for monocytes to investigate if the immunoregulatory role of IL-27 is in part due to effects on major histocompatibility complex (MHC) Ag presentation. We find that IL-27 induces mRNA and surface expression of class II MHC in THP-1 cells. IL-27 also increases class I MHC heavy chain, beta2m, and TAP-1 transcripts, leading to an increased surface expression of class I MHC. In addition, IL-27 enhances expression of costimulatory molecules CD80 and CD86 and adhesion molecule CD54. Expression of the class II transactivator (CIITA) isoforms III and IV, but not I, transcripts increases in response to IL-27. Our data suggest that the pro-inflammatory role of IL-27 is mediated in part through increased expression of key molecules involved in the class II and class I MHC pathways.

Mutualistic fungus Phomopsis liquidambari increases root aerenchyma formation through auxin-mediated ethylene accumulation in rice (Oryza sativa L.).

The fungal endophyte Phomopsis liquidambari can improve nitrification rates and alter the abundance and composition of ammonia-oxidizers in the soil rhizosphere of rice. Aerenchyma is related to oxygen transport efficiency and contributes to the enhanced rhizospheric nitrification under flooding conditions. However, whether and how P. liquidambari affects aerenchyma formation is largely unknown. We therefore conducted pot and hydroponic experiments to investigate the changes of aerenchyma area, ethylene and indole-3-acetic acid (IAA) levels in rice with or without P. liquidambari infection. Our results showed that the larger aerenchyma area in rice roots with P. liquidambari inoculation was associated with markedly up-regulated expression of genes related to aerenchyma formation. Meanwhile, P. liquidambari inoculation substantially elevated root porosity (POR) and radial oxygen loss (ROL), leading to the enhancement of oxidation-reduction potential (ORP) under pot condition. Besides, P. liquidambari significantly increased IAA and ethylene levels in rice by stimulating the expression of genes involved in auxin and ethylene biosyntheses. Furthermore, auxin that partly acting upstream of ethylene signalling played an essential role in P. liquidambari-promoted aerenchyma formation. These results verified the direct contribution of P. liquidambari in promoting aerenchyma formation via the accumulation of IAA and ethylene in rice roots, which provides a constructive suggestion for improving hypoxia tolerance through plant-endophyte interactions.