Organoaluminium complexes of ortho-, meta-, para-anisidines: synthesis, structural studies and ROP of ε-caprolactone (and rac-lactide)

Reaction of Me₃Al (two equivalents) with ortho-, meta- or para-anisidine, (OMe)(NH₂)C₆H₄, affords the complexes {[1,2-(OMe),NC₆H₄(μ-Me₂Al)](μ-Me₂Al)}₂ (1), [1,3-(Me₃AlOMe),NHC₆H₄(μ-Me₂Al)]2 (2) or [1,4-(Me₃AlOMe),NHC₆H₄(μ-Me₂Al)]₂ (3), respectively. The molecular structures of 1–3 have been determined and all three complexes were found to be highly active for the ring opening polymerization (ROP) of ε-caprolactone. 1 was found highly active either with or without benzyl alcohol present; at various temperatures, the activity order 1 > 2 ≈ 3 was observed. For the ROP of rac-lactide results for 1–3 were poor

Evolutionary Analysis of the LAFL Genes Involved in the Land Plant Seed Maturation Program

Seeds are one of the most significant innovations in the land plant lineage, critical to the diversification and adaptation of plants to terrestrial environments. From perspective of seed evo-devo, the most crucial developmental stage in this innovation is seed maturation, which includes accumulation of storage reserves, acquisition of desiccation tolerance, and induction of dormancy. Based on previous studies of seed development in the model plant Arabidopsis thaliana, seed maturation is mainly controlled by the LAFL regulatory network, which includes LEAFY COTYLEDON1 (LEC1) and LEC1-LIKE (L1L) of the NF-YB gene family, and ABSCISIC ACID INSENSITIVE3 (ABI3), FUSCA3 (FUS3), and LEC2 (LEAFY COTYLEDON2) of the B3-AFL gene family. In the present study, molecular evolution of these LAFL genes was analyzed, using representative species from across the major plant lineages. Additionally, to elucidate the molecular mechanisms of the seed maturation program, co-expression pattern analyses of LAFL genes were conducted across vascular plants. The results show that the origin of AFL gene family dates back to a common ancestor of bryophytes and vascular plants, while LEC1-type genes are only found in vascular plants. LAFL genes of vascular plants likely specify their co-expression in two different developmental phrases, spore and seed maturation, respectively, and expression patterns vary slightly across the major vascular plants lineages. All the information presented in this study will provide insights into the origin and diversification of seed plants.National Natural Science Foundation of China (NSFC) [91231105]SCI(E)ARTICLE

Oxidation resistance of graphene-coated Cu and Cu/Ni alloy

The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 \degree C in air for up to 4 hours. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth

Ethyleneglycol tungsten complexes of calix[6 and 8]arenes: Synthesis, characterization and ROP of ε-caprolactone

By varying the reaction conditions, the reaction of [W(eg)₃] (eg = 1,2-ethanediolato) with p-tert-butylcalix[n]areneHn (n = 6 or 8) in refluxing toluene affords, following work-up, a number of products which have been fully characterized. From the reaction of p-tert-butylcalix[6]areneH₆ with one or two equivalents of [W(eg)₃], only the oxo-bridged complex {[W(eg)]₂(μ-O)p-tert-butylcalix[6]arene} (1) could be isolated, whereas the use of four equivalents of [W(eg)₃], in the presence of molecular sieves, afforded {[W(eg)₂]₂p-tert-butylcalix[6]areneH₂}·2MeCN (2); molecules of 2 pack in bi-layers. Under similar conditions, use of one or two equivalents of [W(eg)₃] and p-tert-butylcalix[8]areneH₈ afforded {[W(eg)]₂p-tert-butylcalix[8]arene}·MeCN (3) in which each tungsten centre was bound by four calixarene oxygens. By contrast, the small orange prisms resulting from the use of four equivalents of [W(eg)₃] and p-tert-butylcalix[8]areneH₈ were shown by synchrotron radiation to be a mixture of two isomers (4a/4b·3.5MeCN). In the major isomer {1,2-[W(eg)₂]₂p-tert-butylcalix[8]areneH₄} (4a), two tungsten centres bind to neighbouring sets of phenolate oxygens, whereas in the minor isomer {1,3-[W(eg)₂]₂p-tert-butylcalix[8]areneH₄} (4b), there is a protonated phenolic group between the two pairs of phenolate oxygens bound to tungsten; the major:minor ratio is about 83:17. Use of p-tert-butyltetrahomodioxacalix[6]areneH₆ with two equivalents of [W(eg)₃] resulted in the isolation of {[WO(eg)]₂p-tert-butyltetrahomodioxacalix[6]areneH₂} (5·0.83toluene·MeCN), in which each dimethyleneoxa bridge is bound to an oxotungsten(VI) centre. Complexes 1–5, together with the known complex [W(eg)p-tert-butylcalix[4]arene] (6), have been screened for their ability to ring open polymerize (ROP) ε-caprolactone; for 1, 2 and 5, 6 conversion rates were good (>88%) at 110 °C over 12 or 24 h, whereas the calix[8]arene complexes 3 and 4 under the same conditions were inactive

Patch-Burn Grazing Impacts Forage Resources in Subtropical Humid Grazing Lands

Subtropical humid grazing lands represent a large global land use and are important for livestock production, as well as supplying multiple ecosystem services. Patch-burn grazing (PBG) management is applied in temperate grazing lands to enhance environmental and economic sustainability; however, this management system has not been widely tested in subtropical humid grazing lands. The objective of this study was to determine how PBG affected forage resources, in comparison with the business-as-usual full-burn (FB) management in both intensively managed pastures (IMP) and seminative (SN) pastures in subtropical humid grazinglands. We hypothesized that PBG management would create patch contrasts in forage quantity and nutritive value in both IMP and SN pastures, with a greater effect in SN pastures. A randomized block design experiment was established in 2017 with 16 pastures (16 ha each), 8 each in IMP and SN at Archbold Biological Station\u27s Buck Island Ranch in Florida. PBG management employed on IMP and SN resulted in creation of patch contrast in forage nutritive value and biomass metrics, and recent fire increased forage nutritive value. Residual standing biomass was significantly lower in burned patches of each year, creating heterogeneity within both pasture types under PBG. PBG increased digestible forage production in SN but not IMP pastures. These results suggest that PBG may be a useful management tool for enhancing forage nutritive value and creating patch contrast in both SN and IMP, but PBG does not necessarily increase production relative to FB management. The annual increase in tissue quality and digestible forage production in a PBG system as opposed to once every 3 yr in an FB system is an important consideration for ranchers. Economic impacts of PBG and FB management in the two different pasture types are discussed, and we compare and contrast results from subtropical humid grazing lands with continental temperate grazing lands

Even high normal blood pressure affects live birth rate in women undergoing fresh embryo transfer

STUDY QUESTION Do differences in blood pressure within the normal range have any impacts on the live birth rate (primary outcome) or biochemical pregnancy rate (beta-hCG positivity), clinical pregnancy rate (heart beating in ultrasound), abortion rate and ectopic pregnancy rate (secondary outcomes) of fresh embryo transfer in women undergoing their IVF/ICSI treatment? SUMMARY ANSWER Even rather small differences in baseline blood pressure in women with normal blood pressure according to current guidelines undergoing fresh embryo transfer after IVF/ICSI affects substantially the live birth rate. WHAT IS KNOWN ALREADY Pre-pregnancy hypertension is a well-known risk factor for adverse pregnancy events such as preeclampsia, fetal growth restriction, placental abruption and adverse neonatal events. It is likewise well known that hypertension during pregnancy in women undergoing ART is associated with adverse pregnancy outcomes. However, whether blood pressure at the high end of the normal range has an impact on ART is unknown. STUDY DESIGN, SIZE, DURATION It is a prospective observational cohort study based on a single IVF center between January 2017 and December 2018. PARTICIPANTS/MATERIALS, SETTING, METHODS Two thousand four hundred and eighteen women with normal blood pressure undergoing fresh embryo transfer after IVF/ICSI at the Reproductive and Genetic Hospital of CITIC-Xiangya were enrolled in this study. MAIN RESULTS AND THE ROLE OF CHANCE Blood pressure was measured at the first visit when women consulted the IVF center due to infertility. In women with a successful pregnancy outcome (1487 live births out of 2418 women undergoing fresh embryo transfer after IVF/ICSI), systolic blood pressure (SBP) (114.1 ± 9.48 mmHg versus 115.4 ± 9.8 mmHg, P = 0.001) and diastolic blood pressure (DBP) (74.5 ± 7.5 mmHg versus 75.3 ± 7.34 mmHg, P = 0.006) were lower than in those who did not achieve live births. Multivariate logistic regression analysis revealed that SBP (OR: 0.987, 95% CI: 0.979–0.996, P = 0.004) and DBP (OR: 0.986, 95% CI: 0.975–0.998, P = 0.016) were negatively associated with live birth. Similarly, SBP was significantly negatively related to clinical pregnancy rate (OR: 0.990, 95% CI: 0.981–0.999, P = 0.033), while for DBP the association was not statistically significant (OR: 0.994, 95% CI: 0.982–1.006, P = 0.343). However, both SBP and DBP were positively associated with miscarriage OR: 1.021 (95% CI: 1.004–1.037, P = 0.013) and OR: 1.027 (95% CI: 1.005–1.049, P = 0.014), respectively. Both SBP and DBP were unrelated to biochemical pregnancy (hCG positivity), implantation and ectopic pregnancy rate. LIMITATIONS, REASONS FOR CAUTION Whether lowering blood pressure before initiating ART treatment in women with SBP or DBP higher than the thresholds defined in our study will confer a benefit is unknown. Also, we cannot exclude bias due to different ethnicities. Moreover, participants in our study only received fresh embryo transfer, whether the results could apply to frozen embryo transfer is unclear. WIDER IMPLICATIONS OF THE FINDINGS Our study challenges the current blood pressure goals in women undergoing fresh embryo transfer after IVF/ICSI. Further studies are needed to figure out the mechanism and effective approach to increase IVF/ICSI pregnancy outcomes. STUDY FUNDING/COMPETING INTEREST(S) Hunan Provincial Grant for Innovative Province Construction (2019SK4012). The authors declare that there were no conflicts of interest in this study. TRIAL REGISTRATION NUMBER N/A

Control of intestinal stem cell function and proliferation by mitochondrial pyruvate metabolism.

Most differentiated cells convert glucose to pyruvate in the cytosol through glycolysis, followed by pyruvate oxidation in the mitochondria. These processes are linked by the mitochondrial pyruvate carrier (MPC), which is required for efficient mitochondrial pyruvate uptake. In contrast, proliferative cells, including many cancer and stem cells, perform glycolysis robustly but limit fractional mitochondrial pyruvate oxidation. We sought to understand the role this transition from glycolysis to pyruvate oxidation plays in stem cell maintenance and differentiation. Loss of the MPC in Lgr5-EGFP-positive stem cells, or treatment of intestinal organoids with an MPC inhibitor, increases proliferation and expands the stem cell compartment. Similarly, genetic deletion of the MPC in Drosophila intestinal stem cells also increases proliferation, whereas MPC overexpression suppresses stem cell proliferation. These data demonstrate that limiting mitochondrial pyruvate metabolism is necessary and sufficient to maintain the proliferation of intestinal stem cells

Mono- and tetra-nuclear copper complexes bearing bis(imino)phenoxide derived ligands: catalytic evaluation for benzene oxidation and ROP of epsilon-caprolactone

Complexes of the type [Cu(L)2] (1) and [Cu4L2(μ4−O)(OAc)4] (2) have been obtained from the reaction of the phenoxydiimine 1,3-(2,6-R22C6H3N=CH)2-5-R1C6H2OH-2 (LH) (where R1 = Me, tBu, Cl; R2 = Me, iPr) with copper(II) acetate [Cu(OAc)2]; changing the molar ratio of the reactants affords 10 differing amounts of 1 or 2. Reaction of the parent dialdehyde [1,3-(CHO)2-5-MeC6H2OH-2] with [Cu(OAc)2] in the presence of Et3N afforded, following work-up, a polymeric chain (3) comprising {[Cu2(OAc)4]OAc}n, HNEt3 and MeCN. The crystal structures of 1 (R1 = Me, R2 = iPr 1a; R1 = Cl, R2 = iPr 1b), 2 (R1 = Me, R2 = Me 2a; R1 = Me, R2 = iPr 2b; R1 = tBu, R2 = Me 2c; R1 = Cl, R2 = Me 2d; R1 = Cl, R2 = iPr 2e; R1 = tBu, R2 =iPr 2f) and 3 are reported (synchrotron radiation was necessary for 3). The 15 magnetic properties of the cluster 2b are presented. Complexes of type 2 and 3 were screened for the ring opening polymerization (ROP) of ε-caprolactone, with or without benzyl alcohol present, under a variety of conditions, however only trace polymer was isolated. The electrochemistry of all complexes was also investigated, together with their ability to catalyze benzene oxidation (using hydrogen peroxide); although low conversions were observed, the tetra-nuclear complexes exhibited excellent selectivity