Cobalt‐based metal coordination polymers with 4,4′‐bipyridinyl groups: highly efficient catalysis for one‐pot synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions

Three new metal coordination complexes, namely [Co(BPY)₂(H₂O)₂](BPY)(BS)₂(H₂O)₄ ( 1 ), [Co(BPY)₂(H₂O)₄](ABS)₂(H₂O)₂ ( 2 ) and [Co(BPY)(H₂O)₄](MBS)₂ ( 3 ) (BPY = 4,4′‐bipyridine, BS = phenylsulfonic acid, ABS = p‐aminobenzenesulfonic acid, MBS = p‐methylbenzenesulfonic acid), were obtained under hydrothermal conditions. Complexes 1 , 2 , 3 were structurally characterized using single‐crystal X‐ray diffraction and infrared spectroscopy. All of them display low‐dimensional motifs: complex 1 displays a two‐dimensional structure; and complexes 2 and 3 exhibit a one‐dimensional tape structure. Through strong intermolecular hydrogen bonding interactions and weak packing interactions, all of them further stack to generate a three‐dimensional supramolecular architecture. Catalysts 1 , 2 , 3 were involved in the green synthesis of a variety of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions through Biginelli reactions. The corresponding catalytic product was obtained in quantitative yields (99%) under eco‐friendly synthesis conditions for the variety of reactions. Catalysts 1 , 2 , 3 exhibit excellent efficiency for the desired product, and their catalytic performance shows the following order: 2  >  1  ≈  3 , which can be ascribed to the hydrophobic interactions of different phenylsulfonate groups. The catalytic performance for the Biginelli reaction is not only dependent on the selected solvents, but also inversely proportional to the polarities of the solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Biomimetic design of amphiphilic polycations and surface grafting onto polycarbonate urethane film as effective antibacterial agents with controlled hemocompatibility

The synthetic polycations are ideal candidates as antimicrobial agents, because they resemble natural antimicrobial peptides, but to render hemocompatibility to these materials is a great challenge. Herein, we used 2‐(tert‐butyl‐aminoethyl) methacrylate (TBAEMA), to synthesize its homopolymer and pegylated random and diblock copolymers with polyethyleneglycol methacrylate (PEGMA, M_n = 360 Da) by single‐electron transfer–living radical polymerization (SET‐LRP). In the second step, the secondary amino groups in the precursor polymers were quaternized with iodomethane and bromohexane, to obtain three series of quaternized polymers. The antimicrobial properties of these quaternized polymers were evaluated against Escherichia coli (E. coli), by studying the minimum inhibitory concentrations (MICs) which ranged between 32 and 200 mg L^?1 and showed higher values for the quaternized random than the diblock copolymers. In addition to, we have also demonstrated the grafting of these polycations onto polycarbonate urethane film surfaces, which showed good killing efficacy against E. coli. Furthermore, the hemolysis of these materials was investigated against human red blood cells, which indicated that except the quaternized homopolymers that showed highest hemolysis, all other amphiphilic polycations exhibited very low hemolytic activity. Therefore, our designed materials with controlled structures and functionality, synthesized from cheaply available resources could serve as useful agents in the field of biomedicines and implantable materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3166–3176     

Electrochemical Aptasensor for Zearalenone Based on DNA Assembly and Exonuclease III as Amplification Strategy

A sensitively electrochemical aptasensor was developed to detect zearalenone, utilizing DNA assembly based on hybridization chain reaction to amplify the signal current and exonuclease III to reduce the background current. The linear range 5.0×10⁻⁵ ng/mL-50 ng/mL, and the limit of detection is 0.013 pg/mL. The fabricated aptasensor showed the high specificity toward aflatoxin B1 (AFB1), fumonisin B1 (FB1) and ochratoxin A (OTA), good repeatability and reproducibility. In addition, the average recoveries of spiked corn and beer samples were in the range of 89 % to 102 %. The established method is of great significance in the field of food safety detection.     

Simulating gas–liquid multiphase flow using meshless Lagrangian method

A multiphase flow model has been established based on a moving particle semi‐implicit method. A surface tension model is introduced to the particle method to improve the numerical accuracy and stability. Several computational techniques are employed to simplify the numerical procedure and further improve the accuracy. A particle fraction multiphase flow model is developed and verified by a two‐phase Poiseuille flow. The multiphase surface tension model is discussed in detail, and an ethanol drop case is introduced to verify the surface tension model. A simple dam break is simulated to demonstrate the improvements with various modifications in particle method along with a new boundary condition. Finally, we simulate several bubble rising cases to show the capacity of this new model in simulating gas–liquid multiphase flow with large density ratio difference between phases. The comparisons among numerical results of mesh‐based model, experimental data, and the present model, indicate that the new multiphase particle method is acceptable in gas–liquid multiphase fluids simulation. Copyright © 2014 John Wiley & Sons, Ltd.     

Extraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN film

We studied numerically the temperature dependent extraordinary terahertz transmission through niobium nitride （NbN） film perforated with subwavelength spindle-like apertures. Both the resonant frequency and intensity of extraor- dinary terahertz transmission peaks can be greatly modified by the transition of NbN film from the normal state to the superconducting state. An enhancement of the （~1,0） NbN/magnesium oxide （MgO） peak intensity as high as 200% is demonstrated due to the combined contribution of both the superconducting transition and the excitation of localized surface plasmons （LSPs） around the apertures. The extraordinary terahertz transmission through spindle-fike hole arrays patterned on the NbN film can pave the way for us to explore novel active tuning devices.     

Reaction of 2-Methylsulfonyl-4H-4-chromenones with Nucleophiles

For the synthesis of 2-substituted 4H-4-chromenones, 2-methylsulfonyl-4H-4-chromenones as common intermediate were reacted with nucleophiles such as amines and thiophenol to afford the corresponding 2-substituted adducts in very high yields.     

Synthesis of multi‐functionalized carbonyl compounds by palladium–catalysed γ‐substitution of MBH adducts with activated amides

Catalytic allylic γ‐substitution with Morita‐Baylis‐Hillman (MBH) adducts for creating a new family of unsymmetrical dicarbonyl compounds was presented in this work, in which a variety of allylated amide products were achieved in good yields and high regioselectivity with excellent linear‐to‐branched ratios. Especially, it was found that the Pd/HZNU‐Phos complex exhibited remarkably high activity (with a TON up to 16800) in this transformation between dicarbonyl amides and MBH adducts. In addition, the possibly multisite interaction between multifunctional Pd/HZNU‐Phos catalyst system and substrates might responsible for its exceptionally high efficiency in this reaction.     

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     

Phase fluctuation of self-phase-controlled stimulated Brillouin scattering waves via K8 glass

As stimulated Brillouin scattering (SBS) materials, solids have many advantages such as compactness, innoxiousness, and ease of handling. The SBS threshold and reflectivity of K8 glass, a solid material, are investigated. A SBS phase control experiment using K8 glass to achieve coherent beam combination is performed with a self-phase-control technique below the optical damage threshold. The experimental results show that the short-term phase has been stabilized well with λ/33.8 fluctuation during 256 shots (25.6 s), and that the long-term phase change with non-convective K8 glass is much slower than that with convective HT-70 liquid.