Multi-fluorous-included Counter Anions-based Ionic Copolymers:Synthesis and Enhanced Hydrophobic Adsorption Films on Copper Surface for Super Protection

Three multi-fluorous-carried anions-based ionic copolymers(ICs)including(fluorosulfonyl)imide(FSI-),(trifluorometha-nesulfonyl)imide(TFSI-)and hexafluorophosphate anions(PF6-)(IC[FSI-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis(fluorosulfonyl)amide](IC[TFSI-]),poly{1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis[(trifluoromethyl)sulfonyl]-amide}(IC[PF6-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bishexafluorophosphate]were synthesized with a simple ionic exchange method by using amphiphilic poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bisbromide](IC[Br-])as the intermediate ionic polymer.The chemical srutrcures of the target ICs were characterized by nuclear magnetic resonance(NMR)spectroscopy and Fourier-transform infrared spectroscopy(FTIR).It is shown that the target ICs could be spontaneously adsorbed on copper surface in N,N-dimethflormamide(DMF),and the tight adsorption films were formed on metal surface.The contacting angles suggest that the formed adsorption layers of target ICs on copper surface were characterized with hydrophobic nature.Furthermore,the target ICs-copper chemistry bonding was confirmed by various means.The electrochemistry analysis showed that the target ICs adsorption layers could prevent from copper corrosion in H2SO4solution efficiently,and the maximal anticorrosion efficiency was over 95%at 0.100 g/L.In particular,the target ICs showed 85%or above anticorrosion efficiency for copper at a low concentration of 0.025 g/L,which was greater than the intermediate polymer IC[Br-].In addition,an insight of mixed chemisorption and physisorption of the target ICs on metal surface was analyzed and discussed.

Random Binary Brush Architecture Enhances both Ionic Conductivity and Mechanical Strength at Room Temperature

The ionic conductivity and the mechanical strength are two key factors for the performance of poly（ethylene oxide）（PEO） based polyelectrolytes. However, crystallized PEO suppresses ion conductivity at low temperature and melted PEO has low mechanical strength at high temperature. Here, random binary brush copolymer composed of PEO-and polystyrene（PS）-based side chains is synthesized. PEO crystallinity is suppressed by the introduction of PS brushes. Doping with lithium trifluoromethanesulfonate（Li Tf） induces microphase separation. Due to a random arrangement of the brushes, the microphase segregation is incomplete even at high salt loading, which provides both high ionic conductivity and high mechanical strength at room temperature. These results provide opportunities for the design of polymeric electrolytes to be used at room temperature.

Synthesis and self-assembly of temperature and anion double responsive ionic liquid block copolymers

In this paper, double hydrophilic ionic liquid block copolymers （ILBCs）, poly（N-isopropylacrylamide）-block-poly[1-methyl-3-（2-methacryloyloxy propylimidazo- lium bromine）] （PNIPAM-b-PMMPImB）, were polymerized by two-step reversible addi- tion-fragmentation chain transfer （RAFT） process. The composition and molecular weight distributions of ILBCs were characterized using 1HNMR and gel permeation chromato- graphy （GPC）. The self-assembly and temperature- and anion-responsive behaviors of ILBCs were investigated by UV-Vis spectroscopy, TEM and dynamic light scattering （DLS）. With increasing the concentration of （CF3SO2）2N-, the micellization of self- assembling PNIPAM-b-PMMPImB was induced to form a core-shell structure containing the core with hydrophilic PMMPIm-（CF3SO2）2N- surrounded by the shell of PNIPAM via the anion-responsive properties of ILBCs. However, upon temperature increasing, PNIPAM-b- PMMPImB formed the micelles composing of PNIPAM core and PMMPImB shell. The ionic liquid segment with strong hydrophilic property enhanced the hydrogen bonding interaction which expanded the temperature range of phase transition and increased the lower critical solution temperature （LCST） of the system. These results indicate that ILBCs prepared in this paper have excellent temperature and anion double responsive properties, and may be applied as a kind of potential environmental responsive polymer nanoparticles.

Complex micelles with the bioactive function of reversible oxygen transfer

A complex micelle as a hemoglobin functional model with the biaoactive function of reversible oxygen transfer has been constructed through the hierarchical assembly of the diblock copolymer poly（ethylene glycol）-block- poly（4-vinylpyridine-co-N-heptyl-4-vinylpyridine） （PEG-b-P（4VP-co-4VPHep））, tetrakis（4-sulfonatophenyl）porphinato iron（II） （Fe（II）TPPS） and β-cyclodextrin （β-CD）. The μ-oxo dimer of Fe（II）TPPS was successfully inhibited because the Fe（II）TPPS was included into the cavities of β-CDs through host-guest interaction. Fe（II）TPPS coordinated with pyridine groups functions as the active site to reversibly bind dioxygen. In adition, the host-guest inclusion （β-CD/Fe（II）TPPS） was encapsulated in the hydrophobic core of the complex micelle and tightly fixed by P4VP chains. The hydrophilic PEG blocks stretched in aqueous solution to constitute the shells which stabilize the structure of the complex micelle as well as endow the complex micelle with sufficient blood circulation time. Dioxygen can be bound to the Fe（II）TPPS located in the confined space and excellent reversibility of the binding-release process of dioxygen can be achieved. The quaternary amine N-heptyl-4-vinylpyridine can coerce abundant S2O4^2- ions into the core of the complex micelle to facilitate the self-reduction process. Dioxygen adducts （Fe（II）TPPS（O2）） were effectively protected by the double hydrophobic barriers constructed by the cavity of the cyclodextrin and the core of the complex micelle which enhances the ability to resist nucleophilic molecules. Therefore, the rationally designed amphiphilic structure can work as a promising artificial O2 carrier. Potentially, the complex micelle can be expected to improve the treatment of diseases linked with hypoxia.