Spectral Insights into Microdynamics of Thermoresponsive Polymers from the Perspective of Two-dimensional Correlation Spectroscopy

Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.

Rational synthesis of carbon shell coated polyaniline/ MoS2 monolayer composites for high-performance supercapacitors

Conducting polymers generally show high specific capacitance but suffer from poor rate capability and rapid capacitance decary which greatly limits their practical applications in supercapacitor electrodes. To this end, many studies have focused on improving the overall capacitive performance by synthesizing nanostructured conducting polymers or by depositing a range of coatings to increase the active surface area exposed to the electrolyte and enhance the charge transport efficiency and structural stability. Despite this, simultaneously achieving high specific capacitance, good rate performance, and long cycle life remains a considerable challenge. Among the various two-dimensional （2D） layered materials, octahedral （1T） phase molybdenum disulfide （MoS2） nano- sheets have high electrical conductivity, large specific surface areas, and unique surface chemical characteristics, making them an interesting substrate for the controlled growth of nanostructured conducting polymers. This paper reports the rational synthesis of carbon shell-coated polyaniline （PANI） grown on 1T MoS2 monolayers （MoS2/PANI@C）. The composite electrode comprised of MoS2/ PANI@C with a -3 nm carbon shell exhibited a remarkable specific capacitance of up to 678 F-g-1 （1 mV.s-1）, superior capacity retention of 80% after 10,000 cycles and good rate performance （81% at 10 mV.s-1） due to the multiple synergic effects between the PANI nanostructure and 1T MoS2 substrates as well as protection by the uniform thin carbon shell. These properties are comparable to the best overall capacitive performance achieved for conducting polymers-based supercapacitor electrodes reported thus far.

Further Understanding on the Three Domains of Isotactic Polypropylene by Investigating the Crystalline Morphologies Evolution after Treatment at Different Domains

The introduction of concept of the three domains of isotactic polypropylene（iPP） by Wittmann and Lotz et al. is an important advance in understanding the influence of the melt structures on the crystallization behaviors and consequent properties. To further understand the physical nature of the melt structures, the crystalline structures of i PP after thermal treatment in the three domains are systematically investigated. It is found that after treated at different domains the crystal morphologies, including the sizes and birefringence of spherulitic, the proportion of radial and tangential lamellae, etc., have distinctly different features. Our study reveals that the ＂nuclei＂ at domain II compose of locally ordered chains and the induced memory effect could not be erased under annealing treatment, while the ＂nuclei＂ at domain III compose of crystal fragments, which will aggregate under annealing process. Based on our results, highly schematic diagrams are proposed to illustrate the probable physical characteristics of the melt structures at the three different domains.

Polymers with complicated architectures constructed from the versatile, functional monomer 1-ethoxyethyl glycidyl ether

Because glycidyl(Gly) contains an epoxy and an active hydroxyl group, the Gly unit is difficult to introduce into certain polymeric chains in a controlled manner and usually yields hyperbranched polyglycidyl. Alternatively, the monomer 1-ethoxyethyl glycidyl ether(EEGE), derived from Gly and ethyl vinyl ether, has shown potential for application in polymer chemistry, and homopolymerization of this monomer directly produces linear poly(1-ethoxyethyl glycidyl ether) and further yields linear polyglycidyl. In this review, the initiation system of the EEGE monomer is first discussed in terms of chain transfer to monomers in ring-opening polymerization of epoxides with substituent groups. Then, random copolymerization of EEGE with other epoxides is considered. In addition, because the EEGE units on polymers can be transferred to Gly units and further used to construct copolymers with complicated architectures, the applications of EEGE monomers to block, graft, and hyperbranched copolymers are reviewed. Finally, the synthesis of main chain and terminal functional polyethers by transforming the hydroxyl groups at the polymer end or on the main chain into certain functional groups are also discussed. Chemistry based on EEGE has been proved to be an efficient, versatile route to constructing copolymers containing Gly units and ultimately yielding the target properties and applications.

Sorting Semiconducting Single-Walled Carbon Nanotubes by Water-Soluble Polyfluorene Assisted Electrophoresis and Its Application in Field-effect Transistors

We report a considerably promising method based on agarose gel electrophoresis （AGE） to separate single-walled carbon nanotubes by adding a water-soluble polyfluorene （w-PFO） as surfactant into the agarose gel. In this effective method, the AGE/w-PFO gel network will trap more semiconducting single-walled carbon nanotubes （SWNTs） with the assistance ofw-PFO, for the strong interaction between w-PFO and semiconducting species. The optical absorbance, photoluminescence emission and resonant Raman scattering characterization were used to ver- ify the separation effect. The purity of separated semiconducting species is as high as （98±1）%. The demonstrated field effect transistors give the on/off ratio and mobility about 27000 and 10.2 cm^2·V^-1·s^-1, respectively.