High Performance of PVA Nanocomposite Reinforced by Janus-like Asymmetrically Oxidized Graphene: Synergetic Effect of H-bonding Interaction and Interfacial Crystallization

Chinese Journal of Polymer Science - Macromolecule nanocrystal network and strong interfacial interaction are always beneficial to enhance the mechanical property of polymer-based nanocomposites....     

A Hydrosilylation Approach to Silicon‐Bridged Functional Dipyrromethanes: Introducing Silicon to A New Arena

Two silylene‐spaced ((E)‐vinylsilyl)anthracene‐dipyrromethane dyads have been designed and synthesized by RhCl(PPh₃)₃‐catalyzed hydrosilylation reactions of 5‐methyl‐5′‐(ethynylaryl)dipyrromethanes with (9‐Anthryl)‐dimethylsilane. The complexation studies of dyads toward different anions have also been performed, which reveal that dyads exhibit a highly selective response towards fluoride anion attributable to both hydrogen‐bonding and pentacoordination phenomena. This dual‐mode fluoride recognition event is unprecedented and may pave the way for future developments in the areas of porphyrinoids, organosilicon, polymer, and supramolecular chemistry.     

Rare-earth metal derivatives supported by aminophenoxy ligand: Synthesis,characterization and catalytic performance in lactide polymerization

A library of rare-earth metal derivatives supported by an aminophenoxy ligand was prepared and their catalytic performance in lactide polymerization was investigated. It was found that the synthetic strategy had a profound effect on the formation of aminophenoxy rare-earth metal complexes. Amine elimination between Ln[N(SiMe₃)₂]₃(μ-Cl)Li(THF)₃ (Ln = Yb, Y) and 1 equiv. of the aminophenol [HONH] ([HONH] = ο-OCH₃-C₆H₄NHCH₂(3,5-^tBu₂-C₆H₂-2-OH)) in toluene gave the unexpected heterobimetallic bis(aminophenoxy) rare-earth metal complexes [ON]₂LnLi(THF)₂ (Ln = Yb ( 1 ), Y ( 2 )). When the reactions were carried out in THF and TMEDA, amine elimination produced the aminophenoxy rare-earth metal amide complexes {[ON]LnN(SiMe₃)₂}₂ (Ln = Yb ( 5 ), Y ( 6 )) in ca 85% isolated yields. Complexes 5 and 6 could also be obtained from salt metathesis reaction of {[ON]LnCl(THF)}₂ (Ln = Yb ( 3 ), Y ( 4 )) with NaN(SiMe₃)₂ in a 1:2 molar ratio. In addition, treatment of complexes 3 and 4 with NaOAr (Ar = &bond;C₆H₄-4-^tBu) and (SiMe₃)₂NC(NPrⁱ)₂Na in 1:4 and 1:2 molar ratios provided the corresponding aminophenoxy rare-earth metal derivatives {[ON](μ-OAr)Ln(μ-OAr)Na(THF)₂}₂ (Ln = Yb ( 7 ), Y ( 8 )) and {[ON]Ln[(ⁱPrN)₂CN(SiMe₃)₂]}₂ (Ln = Yb ( 9 ), Y ( 10 )), respectively. These complexes were fully characterized, and their molecular structures were determined using single-crystal X-ray diffraction. Polymerization experiments showed that complexes 1 , 2 , 5 , 6 , 9 and 10 were highly active for the ring-opening polymerization of l -lactide in toluene, and complex 1 promoted l -lactide polymerization in a controlled fashion. The polymerization of rac-lactide initiated by the neutral aminophenoxy rare-earth metal complexes 5 , 6 , 9 and 10 in THF afforded heterotactic polymers.     

Copper Bis(oxazoline)-Catalyzed Enantioselective Alkynylation of Benzopyrylium Ions

The stereocontrolled construction of biologically relevant chromanones and tetrahydroxanthones has been achieved through the addition of alkynes to benzopyrylium trilfates under the influence of copper bis(oxazoline) catalysis. Excellent levels of enantiocontrol (63–98 % ee) are achieved in the addition of a variety of alkynes to an array of chromenones with a hydrogen in the 2-position. Promising levels of enantiocontrol (54–67 % ee) are achieved in the alkynylation of chromenones with esters in the 2-position, generating tertiary ether stereocenters resembling those frequently found in naturally occurring metabolites.     

Cephalotanins A–D,Four Norditerpenoids Represent Three Highly Rigid Carbon Skeletons from Cephalotaxus sinensis

Four polycyclic norditerpenoids, cephalotanins A–D ( 1 – 4 ) representing three unprecedented carbon skeletons with highly rigid ring systems, were isolated from Cephalotaxus sinensis and structurally characterized by a combination of various methods. Compounds 1 and 2 are new skeletal norditerpenoid trilactones, while 3 and 4 are two norditerpenoids featuring different new carbon skeletons. Biosynthetic pathways for 1 – 4 were proposed by involving diverse and very fascinating chemical events with the coexisting cephalotane troponoids as the precursors. Compound 1 exhibited good NF‐κB inhibition with an IC₅₀ value of 4.12±0.61 μΜ.     

Estimating Individual Treatment Effect in Observational Data Using Random Forest Methods

Estimation of individual treatment effect in observational data is complicated due to the challenges of confounding and selection bias. A useful inferential framework to address this is the counterfactual (potential outcomes) model, which takes the hypothetical stance of asking what if an individual had received both treatments. Making use of random forests (RF) within the counterfactual framework we estimate individual treatment effects by directly modeling the response. We find that accurate estimation of individual treatment effects is possible even in complex heterogenous settings but that the type of RF approach plays an important role in accuracy. Methods designed to be adaptive to confounding, when used in parallel with out-of-sample estimation, do best. One method found to be especially promising is counterfactual synthetic forests. We illustrate this new methodology by applying it to a large comparative effectiveness trial, Project Aware, to explore the role drug use plays in sexual risk. The analysis reveals important connections between risky behavior, drug usage, and sexual risk. Supplementary material for this article is available online.