区别滞后酶解离和聚合过程的动力学方法

分析了滞后酶解离-聚合的动力学过程,提出了区分解离和聚合机制的动力学方法。这一方法不仅可用于滞后酶本身的研究,确定滞后酶解离态和聚合态的动力学常数,也可以用于判别变性剂引起寡聚酶的失活过程是否由亚基的解离或聚合所致。

Electrochemical Properties of PP13TFSI-LiTFSI-P（VdF-HFP） Ionic Liquid Gel Polymer Electrolytes

N-Methyl-N-propylpiperidiniumbis（trifluoromethanesulfonyl）imide （PP13TFSI）, bis（triflu- oromethanesulfonyl）imide lithium salt （LiTFSI）, and poly（vinylidene difluoride-co- hexafluoropropylene） （P（VdF-HFP）） were mixed and made into ionic liquid gel polymer electrolytes （ILGPEs） by solution casting. The morphology of ILGPEs was observed by scanning electron microscopy. It was found that the ILGPE had a loosened structure with liquid phase uniformly distributed. The ionic conductivity, lithium ion transference num- bet and electrochemical window were measured by electrochemical impedance spectroscopy, chronoamperometric and linear sweep voltammetry. The ionic conductivity and lithium ion transference number of this ILGPE reached 0.79 mS/cm and 0.71 at room temperature, and the electrochemical window was 0 to 5.1 V vs. Li＋/Li. Battery tests indicated that the ILGPE is stable when being operated in Li/LiFePO4 batteries. The discharge capacity maintained at about 135, 117, and 100 mAh/g at 30, 75, and 150 mA/g rates, respectively. The capacity retentions were almost 100% after 100 cycles without little capacity fading.

Preparation and properties of PEO/LiClO_4/KH560-SiO_2 composite polymer electrolyte by sol-gel composite-in-situ method

Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.

Study on the Ion Association in PVdF-based Gel Polymer Electrolyte

Gel polymer electrolytes based on the poly （vinylidene fluoride） （PVdF） and the electrolyte of LiClO4 in propylene carbonate （PC） were prepared by the solution casting technique. The ionic conductivity of the gel electrolytes was above 10^-3 S ·cm^-1 at 30℃ and was affected by the concentration of lithium salt. Because of the strong coulombiq attractions, the dissolved salt ions might aggregate into ion pairs and multiple ion aggregates. The analysis of DSC and X-ray diffraction revealed that the ions association occurred at higher concentration of lithium salt.

In Vitro Antimicrobial Activity Study of Some New Arginine-based Biodegradable Poly （Ester Urethane）s and Poly （Ester Urea）s

Bactericidal activity of some arginine based biodegradable polymers-PEURs （poly （ester urethane）s） and PEUs （poly （ester urea）s） with low cytotoxicity was studied in in vitro experiments. Various bacterial strains both Gram-positive and Gram-negative were used to explore the bactericidal activity of the cationic polymers. As the test objects, the following microorganisms were used： Bacillus subtilis, Staphylococcus aureus, Mycobacterium album, Pseudomonas fluorescens, Escherichia coli, Actinomyces griseus and Aspergillus niger. The obtained results showed that the new cationic polymers suppressed the growth of the studied microorganisms and the bactericidal activity of the tested cationic polymers strongly depending on their chemical structure.

Modulating composite polymer electrolyte by lithium closo-borohydride achieves highly stable solid-state battery at 25℃

Rational composite design is highly important for the development of high-performance composite polymer electrolytes(CPEs)for solid-state lithium(Li)metal batteries.In this work,Li closo-borohydride,Li_(2)B_(12)H_(12),is introduced to poly(vinylidene fluoride)-Li-bis-(trifluoromethanesulfonyl)imide(PVDF-LiTFSI)with a bound N-methyl pyrrolidone plasticizer to form a novel CPE.This CPE shows superb Li^(+)conduction properties,as evidenced by its conductivity of 1.43×10^(-4) S cm^(-1) and Li^(+)transference number of 0.34 at 25℃.Density functional theory calculations reveal that Li_(2)B_(12)H_(12),which features electron-deficient multicenter bonds,can facilitate the dissociation of LiTFSI and enhance the immobilization of TFSI to improve the Li^(+)conduction properties of the CPE.Moreover,the fabricated CPE exhibits excellent electrochemical,thermal,and mechanical stability.The addition of Li_(2)B_(12)H_(12) can help form a protective layer at the anode/electrolyte interface,thereby preventing unwanted reactions.The above benefits of the fabricated CPE contribute to the high compatibility of the electrode.Symmetric Li cells can be stably cycled at 0.2mA cm^(-2) for over 1200 h,and Li||LiFePO_(4) cells can deliver a reversible specific capacity of 140mAh g^(-1) after 200 cycles at 1C at 25℃ with a capacity retention of 98%.

Coagulation behaviors and in-situ flocs characteristics of composite coagulants in cyanide-containing wastewater:Role of cationic polyelectrolyte

In this paper, composite coagulants （PFS, PFSC05, PFSC1 and PFSC5）, prepared by mixing polyferric sulfate （PFS） and cationic polyelectrolyte （CP） coagulants with different weight percent （Wv） of CP （Wp = 0%, 0.5%, 1% and 5%, respectively）, were adopted to treat cyanide-containing wastewater. PFSC5 exhibited superior coagulation performances at optimal conditions： the removal of total cyanide （TCN） and chemical oxygen demand （COD） was 95%-97% and 50%-55%, respectively. The effects of CP on the properties and structure of flocs were investigated by laser diffraction instrument and small-angle laser light scattering （SALLS）, respectively. The results show that the flocs of PFSC5 have higher growth rate, higher strength factor and lower recovery factor than other flocs. They are also much denser and more uniform owing to the higher fractal dimension （DO and less microflocs （10-100μm）. Furthermore, the dense structure of the PFSC5 flocs can be restored after shear and is more resistant to hydraulic conditions. Particularly, detailed morphology evolution of the flocs was in-situ detected by on-line particle imaging. Due to strong ionic strength in wastewater, the CP in PFSC5 plays a significant role of adsorption, while the main mechanism of CP is electrostatic patch aggregation during the PFSC05 systems.

A strong Lewis acid imparts high ionic conductivity and interfacial stability to polymer composite electrolytes towards all-solid-state Li-metal batteries

The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy density.However,the low ionic conductivity of solid polymer electrolytes and their unstable electrolyte/electrode interfaces have hindered their widespread utilization.To address these critical challenges,a strong Lewis acid(aluminum fluoride(AIF_(3)))with dual functionality is introduced into poly(ethylene oxide)(PEO)-based polymer electrolyte.The AlF;facilitates the dissociation of lithium salt,increasing the iontransfer efficiency due to the Lewis acid-base interaction;further the in-situ formation of lithium fluoride-rich interfacial layer is promoted,which suppresses the uneven lithium deposition and continuous undesired reactions between the Li metal and PEO matrix.Benefiting from our rational design,the symmetric Li/Li battery with the modified electrolyte exhibits much longer cycling stability(over 3600 h)than that of the pure PEO/lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)electrolyte(550 h).Furthermore,the all-solid-state LiFeP04 full cell with the composite electrolyte displays a much higher Coulombic efficiency(98.4%after 150 cycles)than that of the electrolyte without the AlF;additive(63.3%after 150 cycles)at a large voltage window of 2.4-4.2 V,demonstrating the improved interface and cycling stability of solid polymer lithium metal batteries.

Biomimetic brain-like nanostructures for solid polymer electrolytes with fast ion transport

The intrinsic drawbacks of electrolytes and the growth of lithium dendrites limit the development of commercial lithium batteries.To address the aforementioned challenges,a novel biomimetic brain-like nanostructure(BBLN)solid polymer electrolyte was created by manipulating the shape of the incorporated nanoparticles.Our designed BBLN solid polymer electrolyte was created by incorporating spherical core-shell(UIO-66@67)fillers into polymer electrolyte,which is significantly different from traditional polymer-based composite electrolytes.UIO-66@67 spherical nanoparticles are highly favorable to eliminating polymer electrolyte stress and deformation during solidification,indicating a great potential for fabricating highly uniform BBLN solid polymer electrolytes with a substantial number of continuous convolutions.Furthermore,spherical nanoparticles can significantly reduce the crystalline structure of polymer electrolytes,improving polymer chain segmental movement and providing continuous pathways for rapid ion transfer.As a result,BBLN solid polymer electrolyte shows excellent ionic conductivity(9.2×10^(−4)S cm^(−1)),a high lithium transference number(0.74),and outstanding cycle stability against lithium electrodes over 6500 h at room temperature.The concept of biomimetic brain-like nanostructures in this work demonstrates a novel strategy to enhance ion transport in polymerbased electrolytes for solid-state batteries.

“Building-block crosslinking”micelles for enhancing cellular transfection of biocompatible polycations

Incorporating functional ligands and biodegradable bonds into biocompatible low-molecular-weight(LMW)polymers,such as 1.8 kDa poly(ethylenimine)(PEI1.8 k),is a common strategy to improve the properties of LMW polymers including biosafety and delivery efficacy.This study demonstrates the hypothesis that introducing different functional ligands and linked reductive disulfides in PEI 1.8k will achieve superior siRNA transfection efficiency.By incorporating PEI-X(X represents cholesterol(Ch),heptafluorobutyric anhydride(HFBA,F)and 4-carboxyphenylboronic acid(PBA))functional ligands into PEI 1.8k and subsequently crosslinking with each other via disulfide bond links,reductive-responsive PEI-X-SS-X-PEI copolymers were constructed to enhance the cellular transfection via the synergistic effect of the high affinity of Ch,F and PBA to cell membranes and the disulfide reduction triggered intracellular disassembly of micelles and subsequent siRNA release.Extraordinarily,ternary Ch-SS-F-SS-PBA micelles exhibited the strongest siRNA transfection efficiencies in in vitro cell experiments and in vivo animal experiments due to the coordination of enhanced serum stability,promoted cell uptake and endosomal escape,and cell targeting ability.This strategy of constructed multifunctional polymer here we called"building-block crosslinking"showed a simple and smart way to synthesize new materials.Also this strategy of constructing ligands-directed reduction-sensitive micelles improves the transfection efficiency of LMW PEI and provides a valuable insight to develop novel gene delivery systems.

Towards the gemini cation anion exchange membranes by nucleophilic substitution reaction

As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.