Thermal stability of ester linkage in the presence of 1,2,3‐Triazole moiety generated by click reaction

The copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC), so‐called “click” reaction, is one of most useful synthetic strategies to connect two polymer chains. 1,2,3‐Triazole ring (TA) produced by the click reaction has good thermal and chemical stability. However, we observed that block copolymers synthesized by the click reaction showed thermal degradation to give homopolymers when they are thermally annealed at high temperature, which is required for obtaining equilibrium microdomain structure. To investigate the origin of thermal instability of block copolymers, we synthesized model polystyrenes (PSs) using systematically designed bi‐functional atom transfer radical polymerization (ATRP) initiators containing TA. PS including both ester and TA groups showed thermal decomposition at relatively low temperature (e.g., 140 °C). MALDI‐TOF analysis clearly demonstrated that the cleavage site is the ester group adjacent to TA. We also found that the bromine group located at the polymer chain end plays an important role in pyrolysis of ester groups at low temperature. The pyrolysis occurs by syn‐elimination of the ester group. This result implies that the phase behavior of block copolymer synthesized by click reaction should be carefully investigated when high temperature thermal annealing is required. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 427–436     

Gamma function to Beck–Cohen superstatistics

In this paper, we show a mathematical construction of Beck–Cohen superstatistics in the Bayesian point of view with the help of the two representations of a gamma function. Furthermore, it is shown how some results for superstatistics are related to each other.     

Synthesis and molecular modeling study of Cu(Ⅱ) complexes derived from 2-(diphenylmethylene)hydrazinecarbothioamide derivatives with cholinesterase inhibitory activities

Thiosemicarbazones of 2-amino-5-chlorobenzophenone and 3-aminobenzophenone（L¹-L⁴） have been synthesized and their Cu（Ⅱ） complexes（1-4） were afforded via coordination with cupric chloride.All these compounds were characterized by UV-vis and IR spectroscopy together with CHN elemental analysis.NMR spectroscopy was also applied to characterize the ligands.In vitro chohnesterase inhibitory assays for the complexes（1-4） showed IC₅₀ values less than 10μmol/L,with complex 1 exhibiting the most activity,IC₅₀=2.15μmol/L and 2.16μmol/L for AChE and BuChE,respectively. Molecular modeling simulation revealed the binding interaction template for complex 1 with the AChE and BuChE receptors.In DPPH assay,the complexes also showed more in vitro antioxidant activities in comparison to their parent ligands.     

Transfection of Mammalian Cells Using Block Copolypeptide Vesicles

An arginine‐leucine block copolypeptide (R₆₀L₂₀) is synthesized, which is capable of forming vesicles with controllable sizes, able to transport hydrophilic cargo across the cell membrane, and exhibit relatively low cytotoxicity. The R₆₀L₂₀ vesicles also possess the ability to deliver DNA into mammalian cells for transfection. Although the transfection efficiency is lower than that of the commercially available transfection agent Lipofectamine 2000, the R₆₀L₂₀ vesicles are able to achieve transfection with significantly lower cytotoxicity and immunogenicity. This behavior is potentially due to its stronger interaction with DNA which subsequently provides better protection against anionic heparin.

     

Synthesis of 3-Alkylidenecepham-4-carboxylic Acid derivatives by Samarium(II) Iodide Reduction

Samarium(II) iodide promoted reductive deacetoxylation of 7-aminocephalosporanic acid derivatives to synthesize 3-alkylidenecepham-4-carboxylates, which could be valuable intermediates for the synthesis of new cephalosporin antibiotics, was investigated.     

Cationic polymerization of isobutylene at room temperature

This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine

The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]₂ ( 1 ; L =PhC(NtBu)₂) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe₂C₅H₄NSiMe₃]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ ₂( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)₃}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)₂C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography.     

A one-pot tandem synthesis of various 1,2-disubstituted benzimidazoles

A facile method to synthesize various 1,2-disubstituted benzimidazoles is developed. It is suggested that formation of a Meisenheimer adduct between the substrate, amine, and solvent aids the N-arylation process. The generality of the protocol is demonstrated by the efficient reactions involving numerous substituents ranging from electron-withdrawing groups to electron-donating groups.     

Adsorption of uranium ions from aqueous solution by amine-group functionalized magnetic Fe3O4 nanoparticle

The magnetic Fe₃O₄ nanoparticle was functionalized by covalently grafting amine group with (3-aminopropyl) trimethoxy silane, and the Fe₃O₄–NH₂ nanoparticle and the Fe₃O₄ nanoparticle were characterized by Fourier transform infrared, and X-ray diffraction. And the results indicated the amine-group was immobilized successfully on the surface of Fe₃O₄. The adsorption behavior of uranium from aqueous solution by the Fe₃O₄ nanoparticle and the Fe₃O₄–NH₂ nanoparticle was investigated using batch experiments. The pH of initial aqueous solution at 5.0 and 6.0 were in favour of adsorption of uranium, and the adsorption percentage of uranium by the Fe₃O₄ nanoparticle and the Fe₃O₄–NH₂ nanoparticle were 81.2 and 95.6 %, respectively. In addition, the adsorption of uranium ions could be well-described by the Langmuir, Freundlich isotherms and pseudo-second kinetic models. The monolayer adsorption maximum capacity of the Fe₃O₄ nanoparticle and the Fe₃O₄–NH₂ nanoparticle were 85.35 and 268.49 mg/g at 298.15 K, respectively, which indicate the adsorption capacity the Fe₃O₄ nanoparticle was improved by amine functionalization.     

The Two-Dimensional Electrides XONa (X=Mg,Ca) as Novel Natural Hyperbolic Materials

In two-dimensional electrides, anionic electrons are spatially confined in interlayer regions with high density, comparable to metals, and they are highly mobile, just as free electrons, resembling hyperbolic metamaterials with metal-dielectric multilayered structures. In this work, two-dimensional electride materials MgONa and CaONa are proposed as good natural hyperbolic materials. By using the first-principles calculations based on density functional theory (DFT), the electronic structures, stabilities, and optical properties of two-dimensional electride materials XONa (X=Mg, Ca) are investigated. Our results show that they are stable in 1-monolayer (1-ML) structures as well as in bulk states. They exhibit hyperbolic dispersions from visible to near infrared spectral range with high qualities up to about 700, which is two orders-of-magnitude larger than the preceding bulk hyperbolic materials. Numerical results reveal that they exhibit negative refraction with low losses. Their high-quality hyperbolic responses over a wide spectral range pave the way of broad photonic applications as natural hyperbolic materials.