Recent advances in the applications of [1.1.1]propellane in organic synthesis

As a highly strained small molecule, [1.1.1]propellane has been widely used in various synthetic transformations owing to the exceptional reactivity of the central bond between the two bridgehead carbons. Utilizing strain-release approaches, the rapid development of strategies for the construction of bicyclo[1.1.1]pentane (BCP) and cyclobutane derivatives using [1.1.1]propellane as the starting material has been witnessed in the past few years. In this review, we highlight the most recent advances in this field. Accordingly, the reactivity of [1.1.1]propellane can be divided into three pathways, including radical, anionic and transition metal-catalyzed pathways under appropriate conditions.     

Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones

The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.     

全无机卤化铅钙钛矿的结构、热力学稳定性和电子性质

有机-无机杂化卤化铅钙钛矿因具有独特的电子和光学特性,已经成为光电领域最有前途的材料。但是,有机-无机钙钛矿材料及器件稳定性差,限制了其实际应用。与杂化钙钛矿相比,全无机卤化物钙钛矿CsPbX₃(X=Cl,Br,I)显示出更强的热稳定性。全无机卤化物钙钛矿CsPbX₃具有多个晶型,在不同的温度下呈不同相结构。目前,关于CsPbX₃的结构和物理性质仍存在争议。本文我们针对三个晶相α-,β-和γ-CsPbX₃的结构,热力学稳定性和电子性质进行了全面的理论研究。第一性原理计算表明,从高温α相到低温β相,然后再到γ相的相变伴随着PbX₆八面体的畸变。零温形成能计算表明,γ相最稳定,这与实验中γ相为低温稳定相的结论一致。电子性质计算表明,所有CsPbX₃钙钛矿都表现出直接带隙性质,并且带隙值从α相到β相再到γ相逐渐增加。这是由于相变发生时,Pb-X成键强度逐渐减弱,使价带顶能量降低,进而带隙增加。在所有相中,α相结构中较强的Pb-X相互作用,导致了较强的带边色散,使其具有较小的载流子有效质量。     

Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_3 PW_(12)O_(4 O)(PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3 × 10~(-4) S/cm and a storage modulus of 1.1 × 10~7 Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.     

The intragastrointestinal fate of paclitaxel-loaded micelles: Implications on oral drug delivery

The goal of the present study is to elucidate the intragastrointestinal fate of micellar delivery systems by monitoring fluorescently labeled different micelles and the model drug paclitaxel (PTX). Both in vitro and ex vivo leakage studies showed fast PTX release in fluids while micelles remained intact, except in fed-state simulated intestinal fluid and fasted-state pig intestinal fluid, thus referring to the intact absorption of micelles and PTX leakage in the gastrointestinal tract with d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) micelles showing higher stability than other micelles. All groups of micelles were absorbed intact in Caco-2 and Caco-2/HT29-MTX cell models and the absorption of TPGS micelles was found to be higher than other micelles. The transport of the micelles across Caco-2/Raji (1.6%–3.5%), Caco-2 (0.8%–1%), and Caco-2/HT29-MTX (0.58%–1%) cell monolayers further verified the absorption of micelles and their subsequent transport; however, more TPGS micelles transported across cell monolayers than other groups. Moreover, the histological examination also confirmed that micelles entered the enterocytes and were transported to basolateral tissues and TPGS showed the stronger ability of penetration than other groups. Thus, these results are succinctly presenting the absorption of intact micelles in GIT confirmed by imaging evidence with prior leakage of the drug, uptake by enterocytes and the transport of micelles that survive the digestion by enterocytes and mainly by microfold cells in material nature dependent way with TPGS showing better results than other groups. In conclusion, these results identify the mechanism by which the gastrointestinal tract processes micelles and point to the likely use of this approach in the design of micelles-based therapies.     

Ruthenium(II)-catalyzed para-selective CH difluoroalkylation of aromatic aldehydes and ketones using transient directing groups

A Ru(II)-catalyzed para-difluoroalkylation of aromatic aldehydes and ketones with a transient directing group has been developed. It utilizes less expensive ruthenium catalysts and allows facile access to challenging difluoroalkylated aldehydes. The mechanism studies suggest that the distinct coordination mode of ruthenium complex with imine moieties is responsible for para-selectivity.     

Study on LiFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript>/C used as cathode materials for lithium-ion batteries with low Sm component

LiFe_1???x Sm _x PO₄/C cathode materials were synthesized though a facile hydrothermal method. Compared with high-temperature solid-phase sintering, the method can allow for the fabrication of low Sm content (2 %), a scarce and expensive rare earth element, while the presence of an optimized carbon coating with large amount of sp²-type carbon sharply increases the material’s electrochemical performance. The high-rate dischargeability at 5 C, as well as the exchange current density, can be increased by 21 and 86 %, respectively, which were attributed to the fine size and the large cell parameter a/c as much. It should be pointed out that the a/c value will be increased for the LiFePO₄ Sm-doped papered by both of the two methods, while the mechanism is different: The value c is increased for the front and the value a is decreased for the latter, respectively.