Quantitative lithium substitution of carboxyl hydrogens in polyacrylic acid binder enables robust SiO electrodes with durable lithium storage stability

The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.

Synthesis of a Macromer, MPEGAA, Used to Prepare an AMPS-modified Polyacrylic Acid Superplasticizer

A macromer, methoxypolyethylene glycol acrylate （MPEGAA）, was synthesized by direct esterification using methoxypolyethylene glycol （MPEG-1200） and acrylic acid （AA） as the main materials. MPEGAA was then used to prepare a polyacrylic acid superplasticizer modified with 2-acrylamido-2- methylpropane sulfonic acid （AMPS）. A single-factor test was performed to investigate the effects of the molar ratio of acid to alcohol （n（AA）/n（MPEG））, inhibitor amount, catalyst amount, temperature, and time of esterification on the synthesis of MPEGAA. The experimental results showed that the optimal esterification conditions were as follows： n（AA）/n（MPEG）, 3.5：1; amount of hydroquinone （as an inhibitor）, 1.2%; amount of para-toluenesulfonic acid （as a catalyst）, 5.5%; reaction temperature, 95 ~C; and reaction time, 6 h. The AMPS- modified polyacrylic acid superplasticizer prepared under the optimal esterification conditions enabled the achievement and maintenance of high cement dispersibility. At an admixture amount of 0.15%, the cement paste fluidity was initially as high as 300 mm, and then decreased to 315 mm after 1 h and to 290 mm after 2 h.

Synthesis and Properties of an AMPS-Modified Polyacrylic Acid Superplasticizer

A 2-acrylamide-2-methyl propylene sodium sulfonic （AMPS）-modified polyacrylic acid superplasticizer was synthesized using aqueous solution polymerization with the major monomers including the self-made active macromers polyethylene glycol mono-methyl ether acrylate acrylic （MPEGAA）, acrylic acid （AA）, AMPS, and sodium methyl allyl sulfonate （SMAS）. The ratios of the monomers were determined using an orthogonal experiment. This research focused on the effects of the dosages of different macromers, the polymerization conditions, and the length of MPEGAA side chains on the properties of the AMPS-modified polyacrylic acid super-plasticizer. The best polymerization conditions of the AMPS-modified polyacrylic acid superplasticizer are when （n（MPEGAA）：n（SMAS）：n（AMPS）：n（AA） equals 0.1：0.1：0.2：0.65, the molecular weight of monomethoxypolyethylene glycol is 1 200, the initiator ammonium persulfate accounts for 5% of the total mass of the polymerized monomers, the polymerization temperature is 80 ~C, and the reaction time is 4 h. The AMPS-modified polyacrylic acid superplasticizer synthesized in the best conditions exhibited excellent dispersivity and dispersion retainability. When the dosage ratio was 0.24%, the initial fluidity was 400 mm and the fluidity had nearly no loss after 1 h.

The Synthesis Technique of Polyacrylic Acid Superplasticizer

Using water separation technique,acrylic acid （AA） and polyethylene glycol （PEG） 1000,of which the ratio was 1.5,were esterified and the optimum esterification ratio of 90% could be reached under the condition of 110 ℃×3 h.Using polyoxyethylene acrylate macromonomer （PA） prepared in the esterification,AA and sodium methylacryl sulfonate （MAS） as monomers,a copolymer which could be used as superplasticizer was prepared by free radical coolymerization in n（PA）：n（AA）：n（MAS） of 1：7：3.When the synthesis condition was 80 ℃× 5 h,the optimal dosage of initiator was 3.0%-4.0%,the fluidity of cement paste with the samples could reach 270 mm.By analyzing the effect of the content of residual small molecule sulfonic monomer on the properties of sample,n（MAS）/n（PA） was controlled in a range of 2.5-3.8.

Effects of an AMPS-Modified Polyacrylic Acid Superplasticizer on the Performance of Cement-based Materials

A self-made AMPS-modified polyacrylic acid superplasticizer and two others of the same type but with different molecular structures, which are commercially available, are used in this study to investigate the effect of a 2-acrylamide-2-methyl propylene sulfonic （AMPS）-modified polyacrylic acid superplasticizer on the properties of cement-based materials. In the experiments, initial fluidity, 1 and 2 h fluidity over time after admixtion, bleeding rate of the net cement mortar, and adsorption capacity and rate of cement particles are determined by adding different dosages of the three superplasticizers into the cement paste to characterize the dispersivity and the dispersion retention capability of each superplasticizer. Water-reducing rates of three kinds of mortars are simultaneously determined to characterize the water-reducing capacity of each superplasticizer, as well as the 3 and 28 d compressive strengths to characterize the compression resistance. Results show that water-reducing effect and fluidity better maintain the capability of the AMPS-modified polyacrylic acid superplasticizer than the two commercially available polyacrylic acid superplasticizers, and the compressive strengths after 3 and 28 d show significant growth. In conclusion, the effects of water reduction and strengthening of the AMPS-modified polyacrylic acid superplasticizer are evidently better than those of the two commercially available polyacrylic acid superplasticizers.

Effect of Molecular Structure on the Performance of Polyacrylic Acid Superplasticizer

The effects of structure parameters, such as molecular structure, segment kinds, molecular weight, and organic functional groups, on the performance of polyacrylic acid superplasticizer were discussed. According to the differences of chain sections, functional groups, eic, polyacrylic acid superplasticizer could be divided into A, B, C three parts. Among them, A chain section included sulfonic acid groups, B chain section carboxyl groups, C chain section polyester. Polyacrylic acid superplasticizers with different matching of A, B, C chain sections, different length of C chain section and different molecular weights were synthesized by acrylic acid, polyethylene glycol, sodium methyl allylsulfonate; the relation between the molecular structure and perfolxnance was also studied. The expetimental results indicate that the water-reduction ratio increases obviously with the increment of the proportion of sodium methyl allylsulfonate chain section in the molecular; the slump retention increases greatly with the increment of the proportion of acrylic acid chain section; the dispersion of cement particles increases with the increment of the chain length of polyethylene glycol; when the molecular weight is in the range of 5000, the dispersion and slump retentibity increase with the increment of the average molecular weight of polymers.

A new approach for development of vaccine against visceral leishmaniasis: Lipophosphoglycan and polyacrylic acid conjugates

Objective: To determine the antileishmanial vaccine effectiveness of lipophosphoglycan(LPG) and polyacrylic acids(PAA) conjugates on in vivo mice models.Methods: LPG molecule was isolated and purified from large-scale Leishmania donovani parasite culture. Protection efficacies of LPG alone, in combination with Freund's adjuvant, in a physical mixture and in conjugate(consisting of various LPG concentrations) with PAA, were comparatively determined by various techniques, such as cultivation with the micro-culture method, assessment of in vitro infection rates of peritoneal macrophages, determination of parasite load in liver with Leishman-Donovan Units, and detection of cytokine responses.Results: Obtained results demonstrated that the highest vaccine-mediated immune protection was provided by LPG-PAA conjugate due to all parameters investigated. According to the Leishman-Donovan Units results, the sharpest decline in parasite load was seen with a ratio of 81.17% when 35 mg LPG containing conjugate was applied. This value was 44.93% for the control group immunized only with LPG. Moreover, decreases in parasite load were 53.37%, 55.2% and 65.8% for the groups immunized with 10 mg LPG containing LPG-PAA conjugate, a physical mixture of the LPG–PAA, and a mixture of LPG + Freund's adjuvant, respectively. Furthermore, cytokine results supported that Th1 mediated protection occurred when mice were immunized with LPG-PAA conjugate.Conclusions: It has been demonstrated in this study that conjugate of LPG and PAA has an antileishmanial vaccine effect against visceral leishmaniasis. In this respect, the present study may lead to new vaccine approaches based on high immunogenic LPG molecule and adjuvant polymers in fighting against Leishmania infection.

Radiation synthesis and characterization of polyacrylic acid hydrogels

The pH-sensitive polyacrylic acid (PAA) hydrogels were synthesized by gamma-ray irradiation at an am- bient temperature. The influences of dose, monomer concentration, cross-linking agent content, pH, and ionic strength on the swelling ratio (SR) of the PAA hydrogels were investigated in detail. The results show that the SR of the hy- drogel decreases with an increase in the dose, monomer concentration, and cross-linking agent content. In alkaline so- lution, the SR of the hydrogels is much higher than that in acid solution. Also, the ionic strength can influence the SR of the hydrogels. The more the concentration, the lower the

IN SITU INTERFEROMETRIC STUDY ON THE GELATION PROCESS OF POLYACRYLIC ACID GELS

In situ interferometry was used to investigate the gelation process of polyacrylic acid (PAA) gels. The basic principle of the in situ interferometry technique is illustrated. It can give sufficient information for non-destructive and successful investigation of the whole gelation process. The effect of initiator concentration on the gelation process was studied. The polymerization rate of AA increases with increasing initiator concentration. The error arising from the thermal effect in the gelation process can be neglected.

Dynamic Behavior and Mass Transport in Polyacrylic Acid Gel by Dynamic Light Scattering

Dynamic behaviors on polyacrylic acid (PAA) gels and mass (small molecules) transports in the gels have been studied mainly by dynamic light scattering (DLS). The cross-linking degree (fc), monomer concentration (Cm) and temperature of the gels have significant influences on its dynamic behavior and mass transport in the gels. The increase of fc leads to decrease of the mesh sizes of the gels, thus the obstacle of the gels for mass transport is increased. As a result, small molecular diffusion Dk in the gels is decreased. So even if for small molecules, the Dk also is influenced.

Effects of an AMPS-modified Polyacrylic Acid Superplasticizer on the Performance of Concrete Materials

A self-made 2-acrylamide-2-methyl propylene sulfonic （AMPS）-modified polyacrylic acid superplasticizer and two other commercially available superplasticizers with different molecular structures are used in this study to investigate the effect of an AMPS-modified polyacrylic acid superplasticizer on the properties of concrete materials. In the experiments, initial and 1.5 h slumps over time after admixtion are determined by adding different dosages of three superplasticizers into the premixed concrete to characterize the slump loss resistance of the premixed concrete. The water-reducing rates of three different types of concrete are determined to characterize the water-reducing capacity of the concrete with each superplasticizer. The 3, 7 and 28 d compressive strength is determined to characterize the mechanical properties of the concrete with each superplasticizer. In the meanwhile, 1, 1.5 and 2.0 h slump loss rates over time after admixtion are determined by adding different dosages of the three superplasticizers into the high-performance concrete （HPC） to characterize the slump loss resistance of HPC. The 7, 28, 60 and 90 d compressive strength is determined to characterize the compressive properties of HPC with each superplasticizer. The dry shrinkage rates of three different types of HPC are determined with each superplasticizer. Electric flux after standard curing for 56 d and chloride ion diffusion coefficient after curing for 28 d of I-IPC are determined to characterize the impermeability of HPC with each superplasticizer. The cross-section was examined using a scanning electron microscopy （SEM） system. Results demonstrate that the AMPS-modified polyacrylic acid superplasticizer has better water-reducing effect and slump than the two commercially available polyacrylie acid superplasticizers. The AMPS-modified polyacrylic acid superplasticizer also shows significant improvement of the compressive strength, especially in comprehensive performance of HPC. In conclusion, the AMPS-modified polyacrylic acid superplastieizer is particularly suitable for the preparation of HPC.

Synthesis and Properties of Lactic Acid-based Cross-linked Poly(ester-amide)

A novel lactic acid-based cross-linked poly（ester-amide） （LCPEA） was synthesized. The gel fraction of the LCPEA could be modulated by the reaction conditions and it affected the mechanical and thermal properties of the LCPEA. The tensile strength, elastic modulus and bend strength of the LCPEA of 65% gel fraction were 4.65, 136.55 and 39.63 MPa, respectively. The thermal decomposition temperature （50 wt%） of the LCPEA was around 410℃.

Preparation and Properties of pH-Responsive Intelligent Medical Dressing Based on Bacterial Cellulose/Polyacrylic Acid

Bacterial cellulose/polyacrylic acid (BC/PAA) pH-responsive hydrogels were prepared by free-radical polymerization (in situ) using BC as the raw material and AA as the monomer. The hydrogels were loaded with curcumin (Cur) to prepare pH-responsive intelligent medical dressings. The preparation process of the hydrogels was optimized by a single factor and response surface experiment using their swelling degree as an index. The structures of BC/PAA pH-responsive hydrogels were characterized by scanning electron microscope (SEM), Fourier Transform Infrared spectrometer (FTIR), X-ray diffraction (XRD), and tensile tester, and the swelling properties, mechanical properties, bacteriostatic properties, and drug release behavior were investigated. The results showed that the BC/PAA pH-responsive hydrogel has a three-dimensional network structure with the swelling rate up to 1600 g/g, compressive strength of up to 8 KPa, and good mechanical properties, and the drug release behavior was in line with the logistic dynamics model, and it has good inhibitory effects on common pathogens of wound infection: E. coli, S. aureus, and P. aeruginosa.

Oxygen self-doping pyrolyzed polyacrylic acid as sulfur host with physical/chemical adsorption dual function for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with high theoretical capacity and energy density need to solve problems such as the high decomposition energy barrier of Li_(2)S and large volume change of sulfur in the charging process caused by the shuttle effect before practical application.Herein,a green synthesis method is used to prepare polyacrylic acid(PAA)superabsorbent material,and then the pyrolyzed PAA(P/PAA)material is obtained as the positive electrode of Li-S battery.Density functional calculation reveals that the oxygen self-doping pyrolyzed polyacrylic acid(P/PAA)delivered stronger binding energy toward Li2S species in carbonyl C=O than that of graphite powder(GP)which are-1.58 eV and-1.02 eV,respectively.Coupled with the distribution of relaxation time analysis and the in-situ electrochemical impedance approach,it is further demonstrated that the designed P/PAA as sulfur host plays a physical/chemical adsorption dual function in maintaining the stability and rate performance of batteries.With an initial discharge capacity of 1258 mAh/g at 0.1 C and a minimal capacity decline of 0.05%per cycle even after 800 cycles at 0.5 C,the produced cathode demonstrated outstanding electrochemical performance.The average Coulombic efficiency is nearly 100%.The P/PAA electrodes may typically retain 96%of their capacity while declining on average only 0.033%per cycle after 130 cycles at 3 C.This effort provides a new method for the future development of heteroatomic self-doping superabsorbent with promising adsorption properties for polysulfides as cathode materials of Li-S batteries.

An Efficient Extraction-Free Method for Oxidative Desulfurization of Model Fuels Employing Cross-Linked Polyionic Liquid Phosphotungstate Catalysts

An efficient extraction-free oxidative desulfurization(ODS)process using a series of cross-linked polyionic liquid phosphotungstate(CLPIL-PW)catalysts is reported.The cross-linked PILs were prepared with DVB and 1-n-alkyl-3-vinyl imidazole hydrobromide(alkyl=ethyl,butyl,octyl,dodecyl),and were then assembled with phosphotungstic acid(H_(3)PW_(12)O_(40))to form the catalysts.The CLPIL-PWs have been applied to the oxidative removal of dibenzothiophene(DBT)from model oil with H_(2)O_(2) as an oxidant.The effects of ionic liquid(IL)cationic species,varying the DVB/IL molar ratio in the polymerization process,and varying operating conditions were investigated.The CLPIL-PWs were characterized by inductively coupled plasma(ICP)mass spectrometry,elemental analysis,scanning electron microscopy(SEM),Fourier transform infra-red(FTIR)spectroscopy,X-ray diffraction(XRD),^(13)C and^(31)P nuclear magnetic resonance(NMR)spectroscopy.The polydivinylbenzene-co-1-n-octyl-3-vinyl imidazole phosphotungstate(P(DVB-OVIm)PW)exhibited the highest DBT removal efficiency(99.9%)and remarkable recyclability,and could be reused eight times without reducing its activity.Finally,an extraction-free ODS mechanism is proposed.

Effect on rabbits’intraocular structure by cross-linked hyaluronic formations as vitreous substitute

AIM:To develop a new material for retina filling and to investigate its effect on intraocular structure and histocompatibility in rabbit eyes.METHODS:The polymer-derived hyaluronic acid(HA)was formed by UV light cross-linked with N-vinyl-pyrrolidone.Vitrectomy was performed in the rabbits,and then crosslinked HA hydrogels at different concentrations were injected.Intraocular pressure measurements,cornea check-up,and B-ultrasound examination were performed during the follow-up period.After six weeks’follow-up,the rabbits were sacrificed,and both eyes were removed for hematoxylin-eosin(HE)staining,and the polymer materials were observed under electron microscopy.RESULTS:The particle size of the cross-linked HA hydrogels was mainly around at 100 nm.After vitrectomy and injection into vitreous cavity optical coherence tomography showed that the polymeric material HA had no significant effect on the overall thickness of the retina.The intraocular pressure returned to the normal level gradually at week 4.B-ultrasound results revealed that there is no significant change in the eye tissue given to HA material.The pathological and transmission electron microscopy results showed no obvious pathological change in the primary cells and rod cells under the retina tissue.CONCLUSION:HA-based cross-linked biopolymers has good biocompatibility in rabbit eyes,showing a promising potential as vitreous substitutes.

Cross-linking Copolymerization of Acrylic Acid and Multi-armed Cross-linkers

The overall cross-linking copolymerization of acrylic acid and multi-armed cross-linkers are investigated by in situ interferometry. The results show that the more arms the cross-linkers have, the higher the polymerization rate is. However, they also mean the existence of less cross-linking efficiency and some defects in gel network.

铁离子配位聚丙烯酸基芬顿催化纤维的制备及其性能

为改善聚丙烯酸(PAA)纤维的性能,在湿法纺丝过程中基于铁离子配位反应成功制备了可拉伸PAA初生纤维,利用后拉伸以及热定型工艺优化纤维性能,并探究其作为Fenton催化剂在染料废水处理领域的应用。结果表明:相较硫酸铁盐,氯化铁盐配位的PAA纤维具有更为优异的力学性能和尺寸稳定性;后拉伸和热定型工艺可显著提高PAA纤维的力学性能和催化活性,并抑制铁离子的流失,拉伸20倍且在130℃定型的纤维断裂强度为1.42 cN/dtex,与未拉伸纤维相比提高了914.3%,且可在3 min内脱色90%以上的亚甲基蓝(MB),循环使用40次未出现脱色率衰减现象。