Polypeptide‐b‐Poly(Phenyl Isocyanide) Hybrid Rod‐Rod Copolymers: One‐Pot Synthesis,Self‐Assembly,and Cell Imaging

Hybrid rod‐rod diblock copolymers, poly(γ‐benzyl L‐glutamate)‐poly(4‐cyano‐benzoic acid 2‐isopropyl‐5‐methyl‐cyclohexyl ester) (PBLG‐PPI), with determined chirality are facilely synthesized through sequential copolymerization of γ‐benzyl‐L‐glutamate N‐carboxyanhydride (BLG‐NCA) and phenyl isocyanide monomers bearing chiral menthyl pendants using a Ni(cod)(bpy) complex as the catalyst in one‐pot. Circular dichroism and absorption spectra reveal that each block of the block copolymers possesses a stable helical conformation with controlled helicity in solution due to the induction of chiral pendants. The two diastereomeric polymers self‐assemble into helical nanofibrils with opposite handedness due to the different chiral induction of the L‐ and D‐menthyl pendants, confirmed by transmission electron micro­scopy (TEM). Deprotection of the benzyl groups of the PBLG segment affords biocompatible amphiphilic diblock copolymers, poly(L‐glutamic acid)‐poly(4‐cyano‐benzoic acid 2‐isopropyl‐5‐methyl‐cyclohexyl ester) (PLGA‐PPI), that can self‐assemble into well‐defined micelles by cosolvent induced aggregation. Very interestingly, a chiral rhodamine chromophores RhB(D) can be selectively encapsulated into the chiral polymeric micelles, which is efficiently internalized into living cells when directly monitored with a confocal microscope. This contribution will be useful for developing novel rod‐rod biocompatible hybrid block copolymers with a controlled helicity, and may also provide unique chiral materials for potential bio‐medical applications.

     

Formation of Hexagonally Packed Hollow Hoops and Morphology Transition in RAFT Ethanol Dispersion Polymerization

Similar to the traditional self‐assembly strategy, polymerization induced self‐assembly and reorganization (PISR) can produce a myriad of polymeric morphologies through morphology transitions. Besides the chain length ratio (R) of the hydrophobic to the hydrophilic blocks, the chain mobility in the intermediate nano‐objects, which is a requisite for morphology transition, is a determining factor in the formation of the final morphology. Although various morphologies have been fabricated, hexagonally packed hollow hoops (HHHs) with highly ordered internal structure have not, to the best of our knowledge, been prepared by PISR. In this article, the fabrication of HHHs through morphology transition from large compound vesicles to HHHs is reported. HHHs with highly regular internal structure may have significance in theoretical research and practical applications of nanomaterials.

     

Transformations of iodine species inside elliptical channels of AlPO4‐11 crystals at low temperature: a Raman study

Raman spectra of iodine species confined in one‐dimensional elliptical channels of AlPO₄‐11 (AEL) crystals have been studied from room temperature down to −196 °C. As temperature decreases, thermal fluctuations of individual iodine molecules confined in AEL channels are slowed down and they prefer to rotate to channel axis direction, which increases the population of iodine molecules along channel axis (i.e., lying molecules and chains). Such temperature‐driven orientation transformation of iodine molecules is found to be reversible upon heating up to room temperature. The experimental observations are in good agreement with our theoretical simulations by molecular dynamics on low density iodine‐filled AEL crystals. We thus provide a new way to modulate the orientation of iodine molecules in nanochannels, which may have implications in low‐temperature‐sensitive nanoscale devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Phase‐preserved macroscopic visible‐light carpet cloaking beyond two dimensions

Transformation optics, a recent geometrical design strategy of light manipulation with both ray trajectories and optical phase controlled simultaneously, promises an invisibility cloaking device that can render a macroscopic object invisible even to a scientific instrument measuring optical phase. Recent “carpet” cloaks have extended their cloaking capability to broadband frequency ranges and macroscopic scales, but they only demonstrated the recovery of ray trajectories after passing through the cloaks, while whether the optical phase would reveal their existence still remains unverified. In this paper, a phase‐preserved macroscopic visible‐light carpet cloak is demonstrated in a geometrical construction beyond two dimensions. As an extension of previous two‐dimensional (2D) macroscopic carpet cloaks, this almost‐three‐dimensional carpet cloak exhibits three‐dimensional (3D) invisibility for illumination near its center (i.e. with a limited field of view), and its ideal wide‐angle invisibility performance is preserved in multiple 2D planes intersecting in the 3D space. Optical path length is measured with a broadband pulsed‐laser interferometer, which provides unique experimental evidence on the geometrical nature of transformation optics.

     

高中化学优质教学案例中教材分析的现状研究及分析模型建构*

以核心期刊《化学教育》2018-2021年高中化学教学设计及实施类文献为研究对象,在较完备的教材分析视角指引下,采用内容分析法研究优质教学案例中教材分析的现状及特点,在此基础上构建教材分析模型,探索优质教学案例的设计路径。     

A Furan-based Phosphaphenanthrene-containing Derivative as a Highly Efficient Flame-retardant Agent for Epoxy Thermosets without Deteriorating Thermomechanical Performances

In order to reduce greenhouse gas emissions, developing flame retardants from bio-based resources has aroused extensive interest in recent years. In this work, we utilized furfural(biomass) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) to synthesize a biobased co-curing agent(FGD) to combine with 4,4'-diaminodiphenyl methane(DDM) for obtaining a low-phosphorus loading flame-retardant epoxy thermosets. The introduction of FGD decreased the activation energy of the curing progress, enhanced the mechanical properties of the epoxy thermosets, and did not affect the glass transition temperature of the epoxy thermosets. EP-5.0 had a lower thermal degradation rate and a doubled char yield compared with EP-0. The phosphorus content of EP-5.0 was only 0.45 wt%, while EP-5.0 reached the UL-94 V-0 rating with a high LOI value of 32%. Compared with EP-0, the PHRR of EP-2.5 and EP-5.0 decreased by 22.3% and 31.3%, respectively. The SEM results showed that the addition of FGD made the char residues more uniform and denser, which could effectively prevent combustible volatiles from escaping from the degradation area to the flame area and isolate the heat transfer so that the epoxy thermosets had an excellent flame-retardant performance.     

The new synthesis of sulfuryl-bridged triazinane and its selective recognition to SO42−

Research on Chemical Intermediates - A new method has been developed for the synthesis of a cage-like sulfuryl-bridged triazinane molecule HEXS by acidic condensation of a glycoluril analog with...     

Density functional theory study on the reaction mechanism of Ni+-catalysed cyclohexane dehydrogenation

Structural Chemistry - A detailed theoretical analysis of the mechanism of chemical bond activation in cyclohexane catalysed by the atomic transition-metal cation Ni+ was performed by density...     

Hydrothermal synthesis and electrochemical performance of Fe-doped Co hydroxide electrode materials

Journal of Solid State Electrochemistry - In order to meet the growing energy demand, it is of great significance to develop high-performance electrochemical energy storage materials. In this...