Morphology and microphase separation of star copolymers

Star copolymers have attracted significant interest due to their different characteristics compared with diblock copolymers, including higher critical micelle concentration, lower viscosity, unique spatial shape, or morphologies. Development of synthetic skills such as anionic polymerization and controlled radical polymerization have made it possible to make diverse architectures of polymers. Depending on the molecular architecture of the copolymer, numerous morphologies are possible, for instance, Archimedean tiling patterns and cylindrical microdomains at symmetric volume fraction for miktoarm star copolymers as well as asymmetric lamellar microdomains for star‐shaped copolymers, which have not been reported for linear block copolymers. In this review, we focus on morphologies and microphase separations of miktoarm (A_mB_n and ABC miktoarm) star copolymers and star‐shaped [(A‐b‐B)_n] copolymers with nonlinear architecture. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1–21     

Redox‐responsive core cross‐linked micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) by Diels‐Alder reaction for doxorubicin release

Redox‐responsive core cross‐linked (CCL) micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) (PEO‐b‐PFMA) block copolymers were prepared by the Diels‐Alder click‐type reaction. First, the PEO‐b‐PFMA amphiphilic block copolymer was synthesized by the reversible addition‐fragmentation chain transfer polymerization. The hydrophobic blocks of PFMA were employed to encapsulate the doxorubicin (DOX) drug, and they were cross‐linked using dithiobismaleimidoethane at 60 °C without any catalyst. Under physiological circumstance, the CCL micelles demonstrated the enhanced structural stability of the micelles, whereas dissociation of the micelles took place rapidly through the breaking of disulfide bonds in the cross‐linking linkages under reduction environment. The core‐cross‐linked micelles showed fine spherical distribution with hydrodynamic diameter of 68 ± 2.9  nm. The in vitro drug release profiles presented a slight release of DOX at pH 7.4, while a significant release of DOX was observed at pH 5.0 in the presence of 1,4‐dithiothreitol. MTT assays demonstrated that the block copolymer did not have any practically cytotoxicity against the normal HEK293 cell line while DOX‐loaded CCL micelles exhibited a high antitumor activity towards HepG2 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3741–3750     

Effects of ultrasound on the desulfurization performance of hot coal gas over Zn-Mn-Cu supported on semi-coke sorbent prepared by high-pressure impregnation method

Zn-Mn-Cu/SC(U) sorbent was hydrothermally synthesized by ultrasound-assisted high-pressure impregnation method with semi-coke(SC)as support and the mixed solution of zinc nitrate,manganese nitrate and copper nitrate as active component precursors.The desulfurization performances of hot coal gas on the prepared sorbent at a mid-temperature of 500°C were tested in fixed-bed reactor.Morphology and pore structure of the prepared sorbent were also characterized by TEM,N2adsorption/desorption isotherms and XRD.For comparison,the sorbent of Zn-Mn-Cu/SC prepared by conventional high-pressure impregnation was also evaluated and characterized in order to study the effects of ultrasound treatment.Zn-Mn-Cu/SC(U) sorbent prepared by high-pressure impregnation under ultrasound-assisted condition showed a better desulfurization performance than Zn-Mn-Cu/SC.It could remove H2 S from 1000×10-6m3/m3 to 0.1×10-6m3/m3 at 500°C and maintained for 12.5 h with the sulfur capacity of 7.74%,in which both the breakthrough time and sulfur capacity were about 32% and 51% higher than those of Zn-Mn-Cu/SC sorbent.The introduction of ultrasound during high-pressure impregnation process greatly improved the morphology and pore structure of the sorbent.The ultrasonic treatment made particle size of active components smaller and made them more evenly disperse on semi-coke support,which provided more opportunities to contact with H2S in coal-based gases.However,there were no any difference in compositions and existing forms of active components on the Zn-Mn-Cu/SC and Zn-Mn-Cu/SC(U) sorbents.     

Modified Lagrangian vortex method with improved boundary conditions for water waves past a thin bottom‐standing barrier

Herein, the modified Lagrangian vortex method (LVM), a hybrid analytical‐numerical algorithm per se, is devised to simulate the process of vortex formation and shedding from the sharp edge of a zero‐thickness vertical plate under linear water‐wave attack. Application of the Helmholtz decomposition facilitates a convenient switch between the inviscid‐ and viscous‐flow models, thereby enabling easy incorporation of vorticity effects into the potential‐flow calculations for the viscous‐dominated region. In evaluating the potential‐flow component, making good use of the quickly convergent technique with singular basis functions, correctly capturing the singular behavior in velocity fields near the tip of the plate, leads to a considerable reduction of computational burdens and to 12‐decimal‐place accuracy. The viscous correction is carried out via the meshless LVM with improved boundary conditions. Comparisons with previously published results show good agreement. Simulations of vortex generation and evolution illuminate the ability of the present method, and provide a supplement to pertinent experimental works. The hybrid scheme proposed herein allows flexibility for the former LVM and convenience in the code development. Such a compromise fits particularly well for the high‐resolution modeling of sharp‐edged vortex shedding without heavy numerical developments. Copyright © 2014 John Wiley & Sons, Ltd.