Kinetic modeling of simultaneous polycondensation and free radical polymerization for polyurethane/poly(methyl methacrylate) interpenetrating polymer network

A comprehensive kinetic Monte Carlo algorithm has been developed to investigate the formation process of a polyurethane/poly(methyl methacrylate) (PU/PMMA) interpenetrating polymer network (IPN), in which a component independent strategy is proposed to perform the simulation of simultaneous polycondensation and free radical polymerization. An empiric diffusion model based on the mass fraction of polymer is used to quantify the effect of diffusional limitations on MMA polymerization. Results show that the presence of acrylic monomers has little impact on the formation rate of PU, but the presence of the PU network can accelerate the polymerization of MMA. In addition, the effects of component mass ratio, acrylic cross-linker concentration, and [NCO]/[OH] ratio on the IPN formation kinetics are investigated based on the kinetic model. It is believed that the as-developed modeling strategy can be extended to other IPN systems and provide a better understanding of the interactions between chemically independent networks.     

Biocompatible electrospun tactic poly(methyl methacrylate) blend fibers

Uniform and beads free fibers of pristine syndiotactic PMMA (s-PMMA), isotactic PMMA (i-PMMA), and their blends in the ratio of s:i = 3:1, 1:1 and 1:3 were successfully prepared using the electrospinning technique. The tactic PMMA blend fibers showed unique thermal stability and glass transition temperatures compared to their pristine counterparts. An interesting endotherm peak was observed for the s:i = 1:3 electrospun fibers, which might indicate a complex formation between the two tactic PMMAs. Systematic surface functionalities study by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) revealed the interactions between these two tactic PMMAs. Biocompatibility of tactic PMMA and their blend fibers was first time comparably investigated using HeLa as the model mammalian cell line; an intriguing observance was first revealed that the blend fibers showed better biocompatibility than both pristine ones, though the behind mechanism is not well understood yet.     

A New Ferroelectric Phase of YMnO3 Induced by Oxygen‐Vacancy Ordering

Manganese oxides are good candidates of strongly correlated electron materials due to the uniqueness of electronic structure of manganese and the mobility of oxygen among lattice sites under external impacts. Here, we used electron beam as the excitation source to explore the structural evolution of YMnO₃ and identified a new phase under the radiation of electron beam in the transmission electron microscope. Analyses of the electron energy‐loss spectra reveal that this phase originates from ordered oxygen vacancy. We applied the first principles calculation to pick out the optimized stable structure with a lower polarization, and verified its correctness by electron diffraction and image simulations. Analyses of density of states indicate that weak Y–O covalence is favorable for the existence of ferroelectricity, supporting the electrostatic nature of ferroelectricity in the YMnO₃.     

A physical strategy for the preparation of isotactic polypropylene spheres with microsphere and bead–string spherulite morphologies

This study mainly focuses on the formation of isotactic polypropylene (iPP) blend morphologies with microspheres and distinct bead–string spherulites. iPP microspheres have been prepared by a simple and convenient strategy through either an isothermal or a nonisothermal crystallization process based on the macrophase‐separated structure in molten state of iPP/olefin block copolymer (OBC) blend. The dimension of the iPP spheres can be adjusted easily from about 1 µm to >10 µm by controlling the compatibility and annealing conditions. It was found that any of the following three parameters, the molecular structure of OBC (particularly the octene content), molecular weight of iPP, and annealing condition can be rescaled with others in controlling the dimension of the iPP microspheres. The mechanism of the formation of iPP microspheres was studied in detail. Surprisingly, the typical spinodal decomposition morphology with interconnected or thin sheet structure is the precursor of these microspheres. During the subsequent annealing process, it breaks up and further coarsens into spherical structure. In addition, distinct spherulites with a bead–string substructure have been obtained during the isothermal crystallization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40863.     

除草剂吡草胺的合成

以2,6-二甲基苯胺为原料,与多聚甲醛经亲核消除反应生成希夫碱,再与氯乙酰氯加成反应,最后与吡唑缩合转晶得到除草剂原药吡草胺三斜晶形,总收率达71.5%(以2,6-二甲基苯胺计),含量大于97%,该工艺方法简便、易行,具有工业化应用前景。     

Visible Light‐Initiated C(sp3)?Br/C(sp3)?H Functionalization of α‐Carbonyl Alkyl Bromides through Hydride Radical Shift

A new visible light‐initiated 1,5‐hydride radical shift strategy has been developed to enable the one‐step functionalization of both a C(sp³) Br bond and a C(sp³) H bond adjacent to the same carbon atom. This visible light photoredox catalysis offers a mild and straightforward access to diverse five‐membered carbocyclic ring‐fused polycyclic hydrocarbons with high turnover numbers (TONs; up to 4.93×10³) and broad substrate scope.

     

Efficient Catalyst for Both Suzuki and Heck Cross‐Coupling Reactions: Synthesis and Catalytic Behaviour of Geometry‐ Constrained Iminopyridylpalladium Chlorides

A series of geometry‐constrained iminopyridyl‐palladium chlorides were synthesized and characterized. These phosphine‐free palladium complexes were explored for their catalytic activities in both Suzuki and Heck cross‐coupling reactions, achieving turnover numbers as high as 10⁶ towards various aryl bromides, even those containing various functionalities. In addition, the influence of substituents with steric and electronic factors was reflected by the differences observed in their activities.

     

Fabrication of shish-kebab-structured carbon nanotube/poly(ε-caprolactone) composite nanofibers for potential tissue engineering applications

The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electrospun nanofibers were successfully decorated with shish-kebab structure via a self-induced crystallization technique. The topographical features and the mechanical properties of the composite scaffolds were characterized,and the biocompatibility of the material was assessed by using human osteogenic sarcoma osteoblasts(MG-63 cells). The carbon nanotube(CNT) concentration is found to affect the fiber diameter and mechanical properties of electrospun nanofibers and the periodic distance of the shish-kebab architecture. Cellular attachment and proliferation assays reveal that 0.5 wt% CNT-embedded PCL scaffold shows enhanced biocompatibility with MG-63 cells than their counterparts made of neat PCL, and the collagen-like nanotopology provided by the shish-kebab structure further facilitates the cell adhesion and proliferation. The superior interactions between cells and scaffolds demonstrate that the shish-kebab-structured CNTs/PCL nanofibers may be promising candidate for tissue engineering scaffold application.     

Formation of self-organized Zircaloy-4 oxide nanotubes in organic viscous electrolyte via anodization

This work reports the formation of self-organized Zircaloy-4 (Zr-4) oxide nanotubes in viscous organic ethylene glycol (EG) electrolyte containing a small amount of fluoride salt and deionized (DI) water via an electrochemical anodization. The structure, morphology, and composition of the Zr-4 oxide nanotubes were studied using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), EDX, and XPS. SEM results showed that the length of the nanotubes is approximately 13 μm, and TEM results showed that the inner diameter of the Zr-4 oxide nanotubes is approximately 20 nm with average wall thickness of approximately 7 nm. XRD and selected area electron diffraction pattern (SAED) results confirmed that the as-anodized Zr-4 oxide nanotubes have cubic crystalline structure. Both cubic and monoclinic phases were found after annealing of Zr-4 oxide nanotubes. The tubular structure morphology of Zr-4 oxide nanotubes did not remain intact after annealing which is attributed to the elimination of F species from the annealed nanotubes.