Table_1_Acquisition of non-canonical word orders in Mandarin Chinese.DOCX

To better understand Mandarin-speaking children’s acquisition of non-canonical word orders, we tested comprehension and production of Mandarin non-canonical active ba-construction and passive bei-construction, in comparison with canonical active SVO sentences among 180 children between three and 6 years of age. Our results showed that children had more difficulties with bei-construction compared to SVO sentences in both comprehension and production, but early problems of ba-construction only lied in production. We discussed these patterns in connection with two accounts of language acquisition which attribute language development to the maturation of grammar or to the exposure to the input, respectively.</p

Total Synthesis of Scholarisine K and Alstolactine A

The first asymmetric total syntheses of scholarisine K and alstolactine A have been accomplished. Our syntheses feature (1) ring closure metathesis and an intramolecular Heck reaction to construct the 1,3-bridged [3,3,1] bicycle (C–D ring), (2) intramolecular alkylation followed by Fischer indolization to form the basic skeleton of akuammilines, and (3) bioinspired, acid-promoted epoxide opening/lactonization to generate the second lactone ring of alstolactine A. These results provide evidence of a biogenetic relationship between scholarisine K and alstolactine A, which should facilitate the preparation of other akuammiline-type natural products and their derivatives for functional studies

Kinetic Resolution of Axially Chiral 5- or 8‑Substituted Quinolines via Asymmetric Transfer Hydrogenation

An efficient kinetic resolution of axially chiral 5- or 8-substituted quinoline derivatives was developed through asymmetric transfer hydrogenation of heteroaromatic moiety, simultaneously obtaining two kinds of axially chiral skeletons with up to 209 of selectivity factor. This represents the first successful application of asymmetric transfer hydrogenation of heteroaromatics in kinetic resolution of axially chiral biaryls

Asymmetric Hydrogenation of Isoquinolines and Pyridines Using Hydrogen Halide Generated in Situ as Activator

By employing halogenide trichloroisocyanuric acid as a traceless activation reagent, a general iridium-catalyzed asymmetric hydrogenation of isoquinolines and pyridines is developed with up to 99% ee. This method avoids tedious steps of installation and removal of the activating groups. The mechanism studies indicated that hydrogen halide generated in situ acted as an activator of isoquinolines and pyridines

Roll-to-Roll, Dual-Layer Slot Die Coating of Chitin and Cellulose Oxygen Barrier Films for Renewable Packaging

Cellulose and chitin are the two most abundant naturally produced biopolymers and are being extensively studied as candidates for renewable oxygen barrier films used in packaging. It has been shown that bilayers formed from cellulose nanocrystals (CNCs) and chitin nanofibers (ChNFs) exhibit oxygen barrier properties similar to polyethylene terephthalate (PET). However, this prior work explored only coating each layer individually in sequence through techniques such as spray coating. Here, we demonstrate the viability of dual-layer slot die coating of CNC/ChNF bilayers onto cellulose acetate (CA) substrates. The dual-layer slot die method enables significantly lower oxygen permeability versus spray coating while using a roll-to-roll system that applies the bilayer in a single pass. This work discusses suspension properties, wetting, and drying conditions required to achieve well-controlled ChNF/CNC bilayers. Spray-coated bilayer films were on average 25% thinner than the dual-layer bilayer film; however, the thickness-normalized oxygen permeability (OP) of the dual-layer-coated ChNF/CNC bilayer film on CA was 20 times better than that of the spray-coated bilayers. It has been shown that ChNF contributes to the wetting and barrier properties. Values of OP for the slot die-coated bilayers under optimized drying conditions were as low as 1.2 cm3·μm·m–2·d–1·kPa−1, corresponding to a normalized oxygen transmission rate of 0.32 cm3·m–2·d–1 at 23 °C and 50% relative humidity. It is also noted that the adhesive properties of the dual-layer coating are also improved when films are air-dried and that ChNF contributes to the wetting and barrier properties

Harnessing Hot Electrons from Near IR Light for Hydrogen Production Using Pt-End-Capped-AuNRs

Gold nanorods show great potential in harvesting natural sunlight and generating hot charge carriers that can be employed to produce electrical or chemical energies. We show that photochemical reduction of Pt­(IV) to Pt metal mainly takes place at the ends of gold nanorods (AuNRs), suggesting photon-induced hot electrons are localized in a time-averaged manner at AuNR ends. To use these hot electrons efficiently, a novel synthetic method to selectively overgrow Pt at the ends of AuNRs has been developed. These Pt-end-capped AuNRs show relatively high activity for the production of hydrogen gas using artificial white light, natural sunlight, and more importantly, near IR light at 976 nm. Tuning of the surface plasmon resonance (SPR) wavelength of AuNRs changes the hydrogen gas production rate, indicating that SPR is involved in hot electron generation and photoreduction of hydrogen ions. This study shows that gold nanorods are excellent for converting low-energy photons into high-energy hot electrons, which can be used to drive chemical reactions at their surfaces