Mechanism of high Li-ion conductivity in poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network based electrolyte revealed by solid-state NMR

Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.

Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Cross-Linking of Sago Starch with Furan and Bismaleimide via the Diels-Alder Reaction

This research paper describes the synthesis of thermo-reversible cross-linking of sago starch by grafting a furan pendant group(methyl 2-furoate)onto the starch backbone,followed by a Diels-Alder(DA)reaction of the furan functional group with 1,1′-(methylenedi-4,1-phenylene)bismaleimide(BM).The proof of principles was provided by FTIR and 1H-NMR analyses.The relevant FTIR peaks are the carbonyl peak(υC=O sym)at 1721 cm^(−1);the two peaks appeared after DA cross-linking,i.e.,at 1510 cm^(−1)(corresponding toυCH=CH BM aromatic rings,stretching vibrations),and at 1173 cm^(−1)(assigned to cycloadduct(C-O-C,δDA ring))while the^(1)H-NMR result shows evidence for the presence of a furan ring in the starch matrices(in the range ofδ6.3-7.5 ppm).The crosslinked starch product is indeed thermally reversible,as is evident from the appearance of exothermal(DA,temperature range of 50℃-70℃)and endothermal(retro DA,temperature range of 125℃-150℃)transitions in the DSC thermograms.This paper not only proves the thermal reversibility but also demonstrates that the final product properties(chemical,morphology,and thermal stability)can be tuned by varying the annealing temperature,BM intake,and reaction time.

Insights into the swelling process and drug release mechanisms from cross-linked pectin/high amylose starch matrices

Cross-linked pectin/high amylose mixtures were evaluated as a new excipient for matrix tablets formulations,since the mixing of polymers and cross-linking reaction represent rational tools to reach materials with modulated and specific properties that meet specific therapeutic needs.Objective:In this work the influence of polymer ratio and cross-linking process on the swelling and the mechanism driving the drug release from swellable matrix tablets prepared with this excipient was investigated.Methods:Cross-linked samples were characterized by their micromeritic properties(size and shape,density,angle of repose and flow rate)and liquid uptake ability.Matrix tablets were evaluated according their physical properties and the drug release rates and mechanisms were also investigated.Results:Cross-linked samples demonstrated size homogeneity and irregular shape,with liquid uptake ability insensible to pH.Cross-linking process of samples allowed the control of drug release rates and the drug release mechanism was influenced by both polymer ratio and cross-linking process.The drug release of samples with minor proportion of pectin was driven by an anomalous transport and the increase of the pectin proportion contributed to the erosion of the matrix.Conclusion:The cross-linked mixtures of high amylose and pectin showed a suitable excipient for slowing the drug release rates.

Cross-linked polyelectrolyte reinforced SnO_(2)electron transport layer for robust flexible perovskite solar cells

SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and adhesive polyelectrolyte with ethanolamine(EA)and poly-acrylic acid(PAA).The linear PAA was crosslinked by EA,forming a 3D network that stabilized the SnO_(2)nanoparticle dispersion.An organic–inorganic hybrid ETL is developed by introducing the cross-linked PAA-EA into SnO_(2)ETL,which prevents nano particle agglomeration and facilitates uniform SnO_(2)film formation with fewer defects.Additionally,the PAA-EA-modified SnO_(2)facilitated a uniform and compact perovskite film,enhancing the interface contact and carrier transport.Consequently,the PAA-EA-modified PSCs exhibited excellent PCE of 24.34%and 22.88%with high reproducibility for areas of 0.045 and 1.00 cm~2,respectively.Notably,owing to structure reinforce effect of PAA-EA in SnO_(2)ETL,flexible device demonstrated an impressive PCE of 23.34%while maintaining 90.1%of the initial PCE after 10,000 bending cycles with a bending radius of 5 mm.This successful approach of polyelectrolyte reinforced hybrid organic–inorganic ETL displays great potential for flexible,large-area PSCs application.

In situ formed cross-linked polymer networks as dual-functional layers for high-stable lithium metal batteries

Lithium-metal anodes(LMAs)have been recognized as the ultimate anodes for next-generation batteries with high energy density,but stringent assembly-environment conditions derived from the poor moisture stability dramatically hinder the transformation of LMAs from laboratory to industry.Herein,an in situ formed cross-linked polymer layer on LMAs is designed and constructed by a facile thiol-acrylate click chemistry reaction between poly(ethylene glycol)diacrylate(PEGDA)and the crosslinker containing multi thiol groups under UV irradiation.Owing to the hydrophobic nature of the layer,the treated LMAs demonstrate remarkable humid stability for more than 3 h in ambient air(70%relative humidity).The coating humid-resistant protective layer also possesses a dual-functional characterization as solid polymer electrolytes by introducing lithium bis(trifluoromethanesulfonyl)imide in the system in advance.The intimate contact between the polymer layer and LMAs reduces interfacial resistance in the assembled Li/LiFePO_(4)or Li/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cell effectively,and endows the cell with an outstanding cycle performance.

A UV cross-linked gel polymer electrolyte enabling high-rate and high voltage window for quasi-solid-state supercapacitors

Serving as a promising alternative to liquid electrolyte in the application of portable and wearable devices,gel polymer electrolytes(GPEs)are expected to obtain more preferable properties rather than just be satisfied with the merits of high safety and deformability.Here,an easy-operated method is employed to fabricate cross-linked composite polymer membranes used for GPEs assisted by UV irradiation,in which N-doped carbon quantum dots(N-CQDs)and TiO2are introduced as photocatalysts and additives to improve the performances of GPEs.Specifically,N-CQDs participate as a cross-linker to construct the inner porous structure,and TiO2nanoparticles serve as a stabilizer to improve the electrochemical stability of GPEs under high voltage(3.5 V).The excellent thermal and mechanical stability of the membrane fabricated in this work guarantee the safety of the supercapacitors(SCs).This GPE based SC not only exhibits prominent rate performance(105%capacitance retention at the current density of 40A g^(-1))and cyclic stability(85%at 1 A g^(-1)under 3.5 V after 20,000 cycles),but also displays remarkable energy density(42.88 Wh kg^(-1))with high power density(19.3 k W kg^(-1)).Moreover,the superior rate and cycling performances of the as-prepared GPE based flexible SCs under flat and bending state confirm the feasibility of its application in flexible energy storage devices.

A Self-Healing and Nonflammable Cross-Linked Network Polymer Electrolyte with the Combination of Hydrogen Bonds and Dynamic Disulfide Bonds for Lithium Metal Batteries

The self-healing solid polymer electrolytes(SHSPEs)can spontaneously eliminate mechanical damages or micro-cracks generated during the assembly or operation of lithium-ion batteries(LIBs),significantly improving cycling performance and extending service life of LIBs.Here,we report a novel cross-linked network SHSPE(PDDP)containing hydrogen bonds and dynamic disulfide bonds with excellent self-healing properties and nonflammability.The combination of hydrogen bonding between urea groups and the metathesis reaction of dynamic disulfide bonds endows PDDP with rapid self-healing capacity at 28°C without external stimulation.Furthermore,the addition of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMIMTFSI)improves the ionic conductivity(1.13×10^(−4)S cm^(−1)at 28°C)and non-flammability of PDDP.The assembled Li/PDDP/LiFePO_(4)cell exhibits excellent cycling performance with a discharge capacity of 137 mA h g^(−1)after 300 cycles at 0.2 C.More importantly,the self-healed PDDP can recover almost the same ionic conductivity and cycling performance as the original PDDP.

Self-Cross-Linked Tannin-Aminated Tannin Surface Coatings for Particleboard

Aminated tannins were prepared by reacting mimosa condensed tannin extract with ammonia yielding the substitution of many,if not all of the tannin hydroxyl groups with–NH_(2)groups.A tannin-aminated tannin(ATT)particleboard coating was then prepared by reacting raw tannin extract with aminated tannin extract and thus cross-linking the two by substituting tannin’s hydroxyl groups with the–NH_(2)groups on the aminated tannin to form–NH-bridges between the two.The resulting particleboard coating gave encouraging results when pressed at 180℃for 3 min.Conversely,the system in which tannin was reacted/cross-liked with urea(ATU)by a similar amination reaction did not perform as well as the ATT system,and this even when a higher curing temperature and longer hot press time were used.In particular its water repellence was worse probably due to the presence of urea and such a system with lower reactivity.Nonetheless,substituting the tannin–OHs with the urea–NH_(2)groups appeared to also take place.ATT gave better results than ATU as regards water repellence and mechanical resistance as shown by the cross cut test.The ATT system was shown to be between 95%and 98%biosourced.The difference appeared to be due,by TMA analysis,to the much faster formation of the ATT hardened network leading to a better cross-linked polymer coating.The chemical species formed for both the ATT and ATU system were studied by MALDI ToF and CP MAS^(13)C NMR.

The cytosolic isoform of triosephosphate isomerase,ZmTPI4,is required for kernel development and starch synthesis in maize(Zea mays L.)

Triosephosphate isomerase(TPI)is an enzyme that functions in plant energy production,accumulation,and conversion.To understand its function in maize,we characterized a maize TPI mutant,zmtpi4.In comparison to the wild type,zmtpi4 mutants showed altered ear development,reduced kernel weight and starch content,modified starch granule morphology,and altered amylose and amylopectin content.Protein,ATP,and pyruvate contents were reduced,indicating ZmTPI4 was involved in glycolysis.Although subcellular localization confirmed ZmTPI4 as a cytosolic rather than a plastid isoform of TPI,the zmtpi4 mutant showed reduced leaf size and chlorophyll content.Overexpression of ZmTPI4 in Arabidopsis led to enlarged leaves and increased seed weight,suggesting a positive regulatory role of ZmTPI4 in kernel weight and starch content.We conclude that ZmTPI4 functions in maize kernel development,starch synthesis,glycolysis,and photosynthesis.

qSTA2-2,a novel QTL that contributes to seed starch synthesis in Zea mays L.

The seed storage materials accumulate during seed development,and are essential for seed germination and seedling establishment.Here we employed two bi-parental populations of an F2:3 population developed from a cross of improved 220(I220,small seeds with low starch)and PH4CV(large seeds with high starch),as well as recombinant-inbred lines(RILs)of X178(high starch)and its improved introgression line I178(low starch),to identify the genes that control seed storage materials.We identified a total of 12 QTLs for starch,protein and oil,which explained 3.44-10.79%of the phenotypic variances.Among them,qSTA2-1 identified in F2:3 and qSTA2-2 identified in the RILs partially overlapped at an interval of 7.314-9.554 Mb,and they explained 3.44-10.21%of the starch content variation,so they were selected for further study.Fine mapping of qSTA2-2 with the backcrossed populations of ^(I220)/PH4CV in each generation narrowed it down to a 199.7 kb interval that contains 14 open reading frames(ORFs).Transcriptomic analysis of developing seeds from the near-isogenic lines(NILs)of ^(I220)/PH4CV(BC_(5)F_(2))showed that only 11 ORFs were expressed in 20 days after pollination(DAP)seeds.Five of them were upregulated and six of them were downregulated in NIL^(I220),and the differentially expressed genes(DEGs)between NIL^(I220) and NIL^(PH4CV) were enriched in starch metabolism,hormone signal transduction and glycosaminoglycan degradation.Of the eleven NIL^(I220) differential expressed ORFs,ORF4(Zm00001d002260)and ORF5(Zm00001d002261)carry 75%protein sequence similarity,both encodes an glycolate oxidase,were the possible candidates of qSTA2-2.Further analysis and validation indicated that mutation of the qSTA2-2 locus resulted in the dysfunction of ABA accumulation,the embryo/endosperm ratio and the starch and hormone levels.

Night warming increases wheat yield by improving pre-anthesis plant growth and post-anthesis grain starch biosynthesis

Global climate change is characterized by asymmetric warming,i.e.,greater temperature increases in winter,spring,and nighttime than in summer,autumn,and daytime.Field experiments were conducted using four wheat cultivars,namely‘Yangmai 18’(YM18),‘Sumai 188’(SM188),‘Yannong 19’(YN19),and‘Annong 0711’(AN0711),in the two growing seasons of 2019-2020 and 2020-2021,with passive night warming during different periods in the early growth stage.The treatments were night warming during the tillering-jointing(NW_(T-J)),jointing-booting(NWJ-B),and booting-anthesis(NWB-A)stages,with ambient temperature(NN)as the control.The effects of night warming during different stages on wheat yield formation were investigated by determining the characteristics of dry matter accumulation and translocation,as well as sucrose and starch accumulation in wheat grains.The wheat yields of all four cultivars were significantly higher in NW_(T-J)than in NN in the 2-year experiment.The yield increases of semi-winter cultivars YN19 and AN0711 were greater than those of spring cultivars YM18 and SM188.Treatment NW_(T-J)increased wheat yield mainly by increasing the 1,000-grain weight and the number of fertile spikelets,and it increased dry matter accumulation in various organs of wheat at the anthesis and maturity stages by increasing the growth rate at the vegetative growth stage.The flag leaf and spike showed the largest increases in dry matter accumulation.NW_(T-J)also increased the grain sucrose and starch contents in the early and middle grain-filling stages,promoting yield formation.Overall,night warming between the tillering and jointing stages increased the pre-anthesis growth rate,and thus,wheat dry matter production,which contributed to an increase in wheat yield.

Alkali Tolerance of Concrete Internal Curing Agent Based on Sodium Carboxymethyl Starch

Internal curing agents (ICA) based on super absorbent polymer have poor alkali tolerance and reduce the early strength of concrete.An alkali tolerate internal curing agent (CAA-ICA) was designed and prepared by using sodium carboxymethyl starch (CMS) with high hydrophilicity,acrylic acid (AA) containing anionic carboxylic group and acrylamide (AM) containing non-ionic amide group as the main raw materials.The results show that the ratio of CAA-ICA alkali absorption solution is higher than that existing ICA,which solves the low water absorption ratio of the ICA in alkali environment.The water absorption ratio of CAA-ICA in saturated Ca(OH)_(2) solution is 95.8 g·g^(-1),and the alkali tolerance coefficient is 3.4.The application of CAA-ICA in cement-based materials can increase the internal relative humidity and miniaturize the pore structure.The compressive strength of mortar increases up to 12.95%at 28 d,which provids a solution to overcome the reduction of the early strength.

Rice Grains from Slightly Saline Field Exhibited Unchanged Starch Physicochemical Properties but Enhanced Nutritional Values

This study aims to investigate grain quality and nutritional values of rice(Pokkali,a salt-tolerant cultivar;RD73,a new cultivar improved from KDML105 introgressed with Saltol QTL from Pokkali,and KDML105,a moderately salt-susceptible cultivar)grown under non-saline(0.04–0.87 dS/m)and slightly saline(1.08–4.83 dS/m)field conditions.The results revealed that salinity caused significant reduction in grain size but significant increments in reducing sugar and total protein contents in the grains.Nevertheless,the amounts of starch in the grains of KDML105 and Pokkali rice genotypes were unaffected by the stress.The starch granule size distribution was also unaffected by salinity.Interestingly,only starch from Pokkali was significantly diminished in amylose content,from 19.18%to 16.99%.Accordingly,parameters relating to starch gelatinization,retrogradation,and pasting properties of KDML105 and RD73 were unaffected by salinity;only Pokkali showed a significant increase in percentage of retrogradation along with a significant reduction in gelatinization enthalpy.In the saline field,total phenolic content and antioxidant capacity in the grains of all rice cultivars tended to increase,particularly in Pokkali.On average,essential element contents in grains from the saline-treated plants showed a 33%,32%,32%,22%,20%,11%,and 10%increase in total P,N,K,Mg,Zn,Fe,and Ca content,respectively.Interestingly,total Fe content exhibited the greatest percentage of increments in KDML105(187%).Taken together,cultivation of rice in the slightly saline field did not alter its eating and cooking qualities,while enhanced some nutritional properties such as proteins,minerals,and secondary metabolites like phenolic compounds.

Irrigation regimes modulate non-structural carbohydrate remobilization and improve grain filling in rice(Oryza sativa L.)by regulating starch metabolism

Recently developed ‘super’ rice cultivars with greater yield potentials often suffer from the problem of poor grain filling, especially in inferior spikelets. Here, we studied the activities of enzymes related to starch metabolism in rice stems and grains, and the microstructures related to carbohydrate accumulation and transportation to investigate the effects of different water regimes on grain filling. Two ‘super’ rice cultivars were grown under two irrigation regimes of well-watered(WW) and alternate wetting and moderate soil drying(AWMD). Compared with the WW treatment,the activities of ADP glucose pyrophosphorylase(AGPase), starch synthase(StSase) and starch branching enzyme(SBE), and the accumulation of non-structural carbohydrates(NSCs) in the stems before heading were significantly improved, and more starch granules were stored in the stems in the AWMD treatment. After heading, the activities of α-amylase, β-amylase, sucrose phosphate synthase(SPS) and sucrose synthase in the synthetic direction(SSs)were increased in the stems to promote the remobilization of NSCs for grain filling under AWMD. During grain filling, the enzymatic activities of sucrose synthase in the cleavage direction(SSc), AGPase, StSase and SBE in the inferior spikelets were increased, which promoted grain filling, especially for the inferior spikelets under AWMD.However, there were no significant differences in vascular microstructures. The grain yield and grain weight could be improved by 13.1 and 7.5%, respectively, by optimizing of the irrigation regime. We concluded that the low activities of key enzymes in carbon metabolism is the key limitation for the poor grain filling, as opposed to the vascular microstructures, and AWMD can increase the amount of NSC accumulation in the stems before heading, improve the utilization rate of NSCs after heading, and increase the grain filling, especially in the inferior spikelets, by altering the activities of key enzymes in carbon metabolism.

Microwave Assisted Synthesis and Evaluation of Cross-Linked Carboxymethylated Sago Starch as Superdisintegrant

The aim of this study was to modify the sago starch and evaluate its efficacy as tablet disintegrant. Cross-linked car-boxymethylated sago starch (CMSS) was synthesized using native sago starch (SS) and monochloroacetic acid (MCA) with sodium hydroxide in microwave radiation environment. FT-IR analysis of the sample confirmed the carboxy-methylation by showing absorption peak at 1607.2 cm-1. CMSS with degree of substitution (DS) of 0.31 was formed and, it was further evaluated as disintegrant in Ondasetron based tablets. The results revealed that CMSS could be used as disintegrant in tablet formulation in concentration dependant manner.

Differential roles of C-3 and C-6 phosphate monoesters in affecting potato starch properties

The effects of starch phosphate monoester content(SPC),namely C-3(C3P)and C-6 phosphate monoesters(C6P),on the starch properties were investigated using four potato starches with varied SPC/C3P/C6P and two nonphosphorylated maize starches with a similar range of amylose content(AC)as controls.The starch property results showed that a higher SPC is associated with lower turbidity,storage and loss modulus after storage,and water solubility,but higher swelling power(SP)and pasting viscosities.These findings suggested that SPC inhibited molecular rearrangement during storage and starch leaching during heating,and enhanced swelling and viscosities due to increased hydration and water uptake caused by the repulsion effect of phosphate groups and a less ordered crystalline structure.Increased SPC also resulted in lower resistant starch(RS)content in a native granular state but higher RS after retrogradation.Pearson correlations further indicated that SPC/C3P/C6P were positively correlated with peak(r^(2)=0.925,0.873 and 0.930,respectively),trough(r^(2)=0.994,0.968 and 0.988,respectively),and final viscosities(r^(2)=0.981,0.968 and 0.971,respectively).Notably,SPC,mainly C3P,exhibited a significantly positive correlation with SP(r^(2)=0.859)and setback viscosity(r^(2)=0.867),whereas SPC,mainly C6P,showed a weak positive correlation with RS after retrogradation(r^(2)=0.746).However,SPC had no significant correlations with water solubility,turbidity and rheology properties,which were more correlated with AC.These findings are helpful for the food industry to select potato starches with desired properties based on their contents of SPC,C3P,or C6P.

Study on the Soy Protein-Based Adhesive Cross-Linked by Glyoxal

Based on the ESI-MS and ^(13)C-NMR analysis of the forms of glyoxal in acidic and alkaline solutions,the soy-based adhesive cross-linked by glyoxal was prepared in this work.The results showed that glyoxal existed in water in different forms at different pH levels.Under alkaline conditions,glyoxal transformed to glycolate through the intramolecular disproportionation reaction.Under acidic conditions,although some of glyoxal transformed to glycolate as what happened under alkaline conditions,most of glyoxal molecules existed in the form of fiveor six-membered cyclic ether structure.No ethylene tetraol or free aldehyde group was actually detected under these conditions.Although glyoxal reacted with soy protein under both acidic and alkaline conditions,alkaline conditions were more favorable for the improvement of mechanical performance and water resistance of soybased adhesives than acid conditions.

Applications of Crown Ether Cross-Linked Chitosan for the Analysis of Lead and Cadmium in Environmental Water Samples

A new type of crown ether cross-linked chitosan was synthesized by the reaction of chitosan with 4,4′-dibromodibenzo-18-crown-6 (Br-DBC). Its token structure was analyzed with FT-IR and NMR and the adsorption behaviors for lead and cadmium in environmental water samples by FAAS were studied. In addition the best analysis conditions were discussed and the adsorption mechanism was explained. As the enrichment factor is above 100, both recoveries are 94%–106%, the detection limits of lead and cadmium are 0.5μg·L?1 and 0.04 μg·L?1 and the relatively standard deviations of lead and cadmium are 3.1% and 2.8% respectively, this new method was successfully applied to the determination of environmental water samples. This method is fast and simple and it greatly enhances the determination ability of FAAS for lead and cadmium.