Nucleophilic imidoesterification of dicarbonyl compounds with cyanatobenzenes through C-C bond formation

Under neat conditions,an efficient method for synthesis of imidoesters has been developed using cyanatobenzenes and dicarbonyl compounds.Nucleophilic addition spontaneously occurred between the two kinds of materials at room temperature with yields of up to 90%.A mechanism directed towards to the imidoester formation has been proposed.     

Synthesis of novel copolymer：Poly(p-dioxanone-co-L-phenylalanine)

In order to expand the application of poly(p-dioxanone) or PPDO in biomedical area,a series of novel copolymers were synthesized successfully by one-step,melted copolymerization of p-dioxanone(PDO) and L-phenylalanine N-carboxyanhydride(L-Phe-NCA) monomers.With the in-feed molar ratio of L-PheNCA /PDO equal to 1/20,the conversions of the two kinds of monomers were calculated from ~1H NMR. The average molecular weight and polydispersity of the copolymer increase with the increasing reaction time and catalyst concentration.However,the conversions of the two kinds of monomers did not change with the reaction conditions.A three-step mechanism is presented and proved by high resolution ~1H NMR and IR spectrums.     

Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer,smart drug carrier and supramolecular nanoreactor

Owing to their unique broken symmetry, amphiphilic Janus dendrimers and dendons provide fascinating properties for material, biological, pharmaceutical and biomedical applications. The integration of various organometallic moieties into these macromolecules will further offer the opportunity to form complex and intelligent architectures and materials. Here, we report a novel, simple and multifunctional Janus dendron containing redox‐reversible hydrophobic ferrocene (Fc) unit, complexing‐effective 1,2,3‐triazole ligand and biocompatible hydrophilic triethylene glycol termini. Silver and gold nanoparticles were firstly successfully prepared by using the Janus dendron as the reducing agent of Au(III) and Ag(I), and the stabilizer of the corresponding nanoparticles. The redox response of the Fc moiety was then employed to trigger the release of model drug, rhodamine B, encapsulated in supramolecular micelles formed by the self‐assembly of the Janus dendron. Finally, the precise and excellent metal‐complexing ability of the triazole group in this dendron was fully utilized to stabilize a water‐soluble Cu(I) catalyst, forming supramolecular nanoreactors for the catalysis of the copper(I)‐catalyzed azide alkyne cycloaddition click reaction in only water. The multifunctional characteristics of this dendron highlight the potential for organometallic Janus dendrimers and dendrons in the fields of functional materials and nanomedicines.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing‐Phos: Mechanism‐Oriented Divergent Synthesis of Chiral Pyrrolines

The mechanism‐oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide‐derived nonbiarylatropisomer/silver (silver/Xing‐Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis‐Δ(1)‐pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing‐Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)‐pyrrolines, in which an epimerization of the cis‐Δ(1)‐pyrrolines to the trans‐isomers during was revealed.     

Non-recurrence of exp(z)/z

In this paper, we consider the dynamics of the map z→exp(z)/z on the punctured plane C*=C\{0}. We show that for almost every point z ∈ C*, the ω-limit set of z is equal to {0, ∞}. In particular, the map is not recurrent.