Valence-variable Catalysts for Redox-controlled Switchable Ring-opening Polymerization

As a representative class of sustainable polymer materials, biodegradable polymers have attracted increasing interest in recent years. Despite significant advance of related polymerization techniques, realizing high sequence-control and easy-handling in ring-opening (co)polymerizations still remains a central challenge. To this end, a promising solution is the development of valence-variable metal-based catalysts for redox-induced switchable polymerization of cyclic esters, cyclic ethers, epoxides, and CO₂. Through a valence-determined electron effect, the switch between different catalytically active states as well as dormant state contributes to convenient formation of polymer products with desired microstructures and various practical performances. This redox-controlled switchable strategy for controlled synthesis of polymers is overviewed in this Review with a focus on potential applications and challenges for further studies.     

Towards efficient electromagnetic interference shielding performance for polyethylene composites by structuring segregated carbon black/graphite networks

An electromagnetic interference (EMI) shielding composite based on ultrahigh molecular weight polyethylene (UHMWPE) loaded with economical graphite-carbon black (CB) hybrid fillers was prepared via a green and facile methodology, i.e., high-speed mechanical mixing combined with hot compression thus avoiding the assistance of the intensive ultrasound dispersion in volatile organic solvents. In this composite, the graphite-CB hybrid fillers were selectively distributed in the interfacial regions of UHMWPE domains resulting a typical segregated structure. Thanks to the specific morphology of segregated conductive networks along with the synergetic effect of large-sized graphite flakes and small-sized CB nanoparticles, a low filler loading of 7.7 vol% (15 wt%) yielded the graphite-CB/UHMWPE composites with a satisfactory electrical conductivity of 33.9 S/m and a superior shielding effectiveness of 40.2 dB, manifesting the comparable value of the pricey large-aspect-ratio carbon nanofillers (e.g., carbon nanotubes and graphene nanosheets) based polymer composites. More interestingly, with the addition of 15 wt% graphite-CB (1/3, W/W) hybrid fillers, the tensile strength and elongation at break of the composite reached 25.3 MPa and 126%, respectively; with a remarkable increase of 58.1% and 2420% over the conventional segregated graphite/UHMWPE composites. The mechanical reinforcement could be attributed to the favor of the small-sized CB particles in the polymer molecular diffusion between UHMWPE domains which in turn provided a stronger interfacial adhesion. This work provides a facile, green and affordable strategy to obtain the polymer composites with high electrical conductivity, efficient EMI shielding, and balanced mechanical performance.     

Analytic soliton solutions of cubic‐quintic Ginzburg‐Landau equation with variable nonlinearity and spectral filtering in fiber lasers

In fiber lasers, the study of the cubic‐quintic complex Ginzburg‐Landau equations (CGLE) has attracted much attention. In this paper, four families (kink solitons, gray solitons, Y‐type solitons and combined solitons) of exact soliton solutions for the variable‐coefficient cubic‐quintic CGLE are obtained via the modified Hirota method. Appropriate parameters are chosen to investigate the properties of solitons. The influences of nonlinearity and spectral filtering effect are discussed in these obtained exact soliton solutions, respectively. Methods to amplify the amplitude and compress the width of solitons are put forward. Numerical simulation with split‐step Fourier method and fourth‐order Runge‐Kutta algorithm are carried out to validate some of the analytic results. Transformation from the variable‐coefficient cubic‐quintic CGLE to the constant coefficients one is proposed. The results obtained may have certain applications in soliton control in fiber lasers, and may have guiding value in experiments in the future.

     

New dispersive solid phase extraction sorbent of graphitic carbon nitride for field evaluation and dissipation kinetics of pesticides in wheat ecosystem by liquid chromatography tandem mass spectrometry

Nanosheets of graphitic carbon nitride (GCN) were used as the dispersive solid-phase extraction (d-SPE) sorbent for the first time. GCN successfully purified complex matrices of soil, wheat, and wheat straw utilising a simple QuEChERS (quick, easy, cheap, effective, rugged, and safe) method with liquid chromatography tandem mass spectrometry. Pesticides recoveries in the range of 80–110%, small matrix effect, and decreased amounts guaranteed and distinguished this new sorbent. The application of a real formulation of pesticides under field conditions during 2015 in the wheat ecosystem illustrated the clean-up effect and application potential of GCN. It is a valuable and potential substitute for C18 according to the results comparison between two sorbents, including recoveries, matrix-matched calibration, and dissipation kinetics of pesticides. The new use of GCN also enriched the knowledge of d-SPE and sample preparation furthermore.     

Synthesis of novel cyclohexanediol-derived chiral phosphite ligands and their application in the Cu-catalyzed conjugate addition of organozinc to cyclic enones

A series of novel chiral diphosphite ligands have been synthesized from (1R,2R)-trans-1,2-cyclohexanediol, (1S,2S)-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[(R)-1,1'-binaphthyl-2,2'-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand (1R,2R)-bis[(R)-1,1'-binaphthyl-2,2'-diyl]phosphitecyclohexanediol 6a' derived from enantiopure startingmaterial. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.     

肺炎支原体肺炎患儿急性期和恢复期血浆H-ficolin和L-ficolin水平分析

目的了解肺炎支原体肺炎患儿急性期和恢复期血浆中H-ficolin、L-ficolin水平的变化。方法采用ELISA法检测85例肺炎支原体肺炎患儿急性期和恢复期血浆H-ficolin、L-ficolin水平,并进行相关性分析。结果急性期H-ficolin水平1.8~25.2μg/ml,平均（11.9±5.9）μg/ml,恢复期H-ficolin水平0.3~26.5μg/ml,平均（10.1±5.7）μg/ml,急性期明显高于恢复期（Z=2.161,P=0.031）。急性期L-ficolin水平0.2~10.6μg/ml,平均（4.5±2.3）μg/ml,恢复期L-ficolin水平0.03~10.2μg/ml,平均（4.6±2.2）μg/ml,急性期和恢复期无统计学差异（t=0.245,P=0.807）。患儿急性期血浆H-ficolin水平与L-ficolin水平明显相关（r=0.22,P=0.039）。结论H-ficolin可能参与儿童肺炎支原体肺炎疾病过程。     

Effects of gamma irradiation and accelerated aging on GO/UHMWPE nanocomposites

This article investigates irradiated and accelerated aged graphene oxide (GO)/ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites. The prepared GO/UHMWPE nanocomposites are gamma-irradiated at a high irradiation dose in a vacuum and then accelerated aging procedure is performed at 80°C in an air oven for 21 days. Irradiated and aged samples are characterized by Raman spectrum, Fourier transform infrared (FT-IR) spectrum, differential scanning calorimetry, contact angle, and gel content. Filling GO reduces the intensity of Raman spectrum of UHMWPE and irradiation or aging cannot affect vibrational modes of UHMWPE and GO/UHMWPE. The result of the FT-IR spectrum shows that UHMWPE and GO/UHMWPE basically have the same oxidation index values, whether with irradiation or accelerated aging. Irradiation or aging can slightly increase the melting temperature. GO, irradiation, or aging can significantly increase the crystallinity and improve wetting properties. In irradiated GO/UHMWPE, GO is able to maintain the efficiency of the cross-linking. However, after aging, the cross-linking density of GO/UHMWPE is reduced significantly. According to the above results, it is proposed that GO shows a very weak scavenging free radicals capacity in GO/UHMWPE composites and cannot display antioxidant capacity.     

Syntheses and electrochemical properties of three supramolecular architectures based on Keggin silicontungstates and different metal-organic units

Three new compounds [Mn(H₂O)₂(bimb)₂(H₃SiW₁₂O₄₀)₂](bimb)₄ (1), [Zn₂(bimb)₄(H₂O)₄][SiW₁₂O₄₀] (2), and [Ni₂(bimb)₄(H₂O)₄][SiW₁₂O₄₀] (3) (bimb = 1,3-bis(1-imidazoly)benzene) have been synthesized under the same hydrothermal reaction except for tuning the metal cations (Mn²⁺, Zn²⁺, and Ni²⁺). Structural characterizations show that the three compounds possess distinct structural motives. Compound 1 displays a supramolecular one-dimensional (1 D) chain formed by π···π interactions that occur among the almost parallel bimb ligands from adjacent [Mn(H₂O)₂(bimb)₂(SiW₁₂O₄₀)₂] dimers. Compound 2 shows a supramolecular two-dimensional (2D) layer achieved by intermolecular (C–H···O) hydrogen bondings between the Zn₂(bimb)₄ molecular loops and the SiW₁₂ anions. Compound 3 also exhibits a supramolecular 2D layer, but it is different from 2, which is generated by the π···π interactions among adjacent 1D polymeric chains. The distinct structural features of the three compounds suggest that the metal cations should play a significant role in the process of assembly. Additionally, the electrochemical properties of compounds 1–3 have been investigated, and the results indicate that compounds 1–3 possess excellent electrocatalytic activity toward reduction of both iodated and nitrite molecules.