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     

Synthesis,Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems

A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π‐molecular orbitals.     

考虑运动受限的履带式移动机器人轨迹跟踪控制

针对履带式移动机器人的轨迹跟踪控制问题进行研究,首先,建立了履带式移动机器人的运动学模型和跟踪误差模型；其次,设计了转速有限时间控制和线速度滑模控制的轨迹跟踪控制律,并给出了考虑运动受限作用下的控制律修正表达式；最后,基于MATLAB对所提控制律进行仿真,对比分析了不考虑运动受限情况下跟踪控制效果;结果表明,设计的跟踪控制律能够实现履带式移动机器人对圆轨迹的有效跟踪,且考虑运动受限作用的控制律更加符合实际;文章研究分析了运动受限作用对于移动机器人轨迹跟踪控制的影响,分析结果对其他移动机器人的运动控制研究具有参考价值。     

Isomers of B←N-Fused Dibenzo-azaacenes: How B←N Affects Opto-electronic Properties and Device Behaviors?

The B←N unit has a large dipole and it is isoelectronic to C−C moiety with no dipole. Incorporating B←N units into π-conjugated system is a powerful strategy to design organic small molecules and polymers with intriguing opto-electronic properties and excellent opto-electronic device performance. However, it is unclear how the B←N unit affects electronic structures and opto-electronic properties of large π-conjugated molecules. In this work, to address this question, we developed three dibenzo-azaacene molecules in which two B←N units were introduced at different positions. Although the dibenzo-azaacene skeleton is fully π-conjugated, the effect of B←N unit on the electronic structures of the adjacent rings is much stronger than that of the distant rings. As a result, the three molecules with isomerized B←N incorporation patterns possess different electronic structures and exhibit tunable opto-electronic properties. Among the three molecules, the centrosymmetrical molecule exhibits higher LUMO/HOMO energy levels than those of the two axisymmetrical molecules. When used as the active layer in organic field-effect transistors (OFETs), while the two axisymmetrical molecules show unipolar electron transporting property, the centrosymmetrical molecule exhibits ambipolar hole and electron transporting behavior. This work not only deepens our understanding on organoboron π-conjugated molecules, but also indicates a new strategy to tune opto-electronic properties of organic semiconductors for excellent device performance.     

A New Synthesis for Methyl 2-Benzyloxylphenylacetate

A new synthetic method for methyl 2-benzyloxylphenylacetate, a key intermediate of a new type of fungicides, had been found, which has only 3 steps. The 80% yield of the new method is a major improvement over the 30% 6-step-process reported by the literature.