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.

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.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

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.

A Sustainable Dual Cross‑Linked Cellulose Hydrogel Electrolyte for High‑Performance Zinc‑Metal Batteries

Aqueous rechargeable Zn-metal batteries(ARZBs)are considered one of the most promising candidates for grid-scale energy storage.However,their widespread commercial application is largely plagued by three major challenges:The uncontrollable Zn dendrites,notorious parasitic side reactions,and sluggish Zn^(2+) ion transfer.To address these issues,we design a sustainable dual crosslinked cellulose hydrogel electrolyte,which has excellent mechanical strength to inhibit dendrite formation,high Zn^(2+) ions binding capacity to suppress side reaction,and abundant porous structure to facilitate Zn^(2+) ions migration.Consequently,the Zn||Zn cell with the hydrogel electrolyte can cycle stably for more than 400 h under a high current density of 10 mA cm^(−2).Moreover,the hydrogel electrolyte also enables the Zn||polyaniline cell to achieve high-rate and long-term cycling performance(>2000 cycles at 2000 mA g^(−1)).Remarkably,the hydrogel electrolyte is easily accessible and biodegradable,making the ARZBs attractive in terms of scalability and sustainability.

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 0.5 μg·L -1and 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.

A short-term study of corneal collagen cross-linking with hypo-osmolar riboflavin solution in keratoconic corneas

AIM: To report the 3mo outcomes of collagen crosslinking(CXL) with a hypo-osmolar riboflavin in thin corneas with the thinnest thickness less than 400 μm without epithelium.METHODS: Eight eyes in 6 patients with age 26.2±4.8y were included in the study. All patients underwent CXL using a hypo-osmolar riboflavin solution after its de-epithelization. Best corrected visual acuity, manifest refraction, the thinnest corneal thickness, and endothelial cell density were evaluated before and 3mo after the procedure.RESULTS: The mean thinnest thickness of the cornea was 408.5 ±29.0 μm before treatment and reduced to369.8 ±24.8 μm after the removal of epithelium. With the application of the hypo-osmolar riboflavin solution, the thickness increased to 445.0 ±26.5 μm before CXL and recover to 412.5 ±22.7 μm at 3mo after treatment, P =0.659). Before surgery, the mean K-value of the apex of the keratoconus corneas was 57.6 ±4.0 diopters, and slightly decreased(54.7±4.9 diopters) after surgery(P =0.085). Mean best-corrected visual acuity was 0.55 ±0.23 logarithm of the minimal angle of resolution, and increased to 0.53±0.26 logarithm after surgery(P =0.879).The endothelial cell density was 2706.4 ±201.6 cells/mm2 before treatment, and slightly decreased( 2641. 2 ±218.2 cells/mm2) at last fellow up(P =0.002).CONCLUSION: Corneal collagen cross-linking with a hypo-osmolar riboflavin in thin corneas seems to be a promising treatment. Further study should be done to evaluate the safety and efficiency of CXL in thin corneas for the long-term.

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.

Experimental study on the treatment of rabbit corneal melting after alkali burn with Collagen cross-linking

AIM: To evaluate the effect of Collagen cross-linking on the prevention of melting in rabbit corneas after alkali burn. · METHODS: Twenty New Zealand white rabbits were randomly divided into model control group and collagen cross-linking treatment group. The second group of rabbits received collagen cross linked treatment. Both groups were applied with antibiotic eye drops to prevent infection. The corneas were evaluated for melting, opacity, pathological and immunohistochemistry, record the changes when 28 days after the animals were killed. · RESULTS: In the control group, 6 out of 8 rabbits showed corneal melting after injury (14±4) days, while two corneal perforated. In collagen cross-linking treatment group, one rabbit showed corneal melting after injury 23 days, without corneal perforation; corneal dissolution rate between the two groups was significantly different (P <0.05). Pathological examination suggested that in the treatment group, mild corneal edema, mild damage to collagen fibers, inflammatory cell infiltration was significantly less than the control group. Immunohistochemistry showed that corneal collagen fibers arranged in neat rows in the control group. · CONCLUSION: Collagen cross-linking treatment not only can prevent and delay the corneal melting after alkali burn, but also can reduce the destruction of corneal collagen fibers and infiltration of inflammatory cells in the corneal tissue.

PERVAPORATION PROPERTIES OF PDMS MEMBRANES CURED WITH DIFFERENT CROSS-LINKING REAGENTS FOR ETHANOL CONCENTRATION FROM AQUEOUS SOLUTIONS

Ethanol perm-selective PDMS/PVDF composite membranes were prepared by curing polydimethylsiloxane (PDMS) with various cross-linking reagents,such as tetraethoxylsilane(TEOS),γ-aminopropyltriethoxylsilane(APTEOS), phenyltrimethoxylsilane(PTMOS) and octyltrimethoxylsilane(OTMOS) as well.The cross-linking density and surface properties of the PDMS active layer were adjusted by varying cross-linking reagents.The pervaporation performance of PDMS membranes cured with different cross-linking reagents was inves...

Systematic review and Meta-analysis comparing modified cross-linking and standard cross-linking for progressive keratoconus

AIM: To compare the effectiveness and safety between modified cross-linking(MC) and standard cross-linking(SC) in mild or moderate progressive keratoconus.METHODS: Eligible studies were retrieved from four electronic databases, including CENTRAL, Clinical Trials gov, Pup Med and OVID MEDLINE. We set post-surgical maximum K value(Kmax) as the primary outcome. In addition, uncorrected and corrected distant visual acuity(UDVA and UDVA), spherical equivalent(SE), endothelial cell density(ECD), central cornea thickness(CCT) and depth of demarcation line(DDL) were Meta-analyzed as secondary outcomes. Mean differences for these outcomes were pooled through either a random-effect model or fixed-effect model according to data heterogeneity.RESULTS: Twenty-four comparative studies either on accelerated cross-linking(AC) compared with SC or on transepithelial cross-linking(TC) compared with SC were included and pooled for analysis. The results indicated that MC was significantly inferior to SC at delaying Kmax deterioration [AC vs SC 0.49(95% CI: 0.04-0.94, I^2=75%, P=0.03); TC vs SC 1.15(95% CI: 0.54-1.75, I^2=50%, P=0.0002)]. SE decreased significantly for SC when compared to AC [0.62(95% CI: 0.38-0.86, I^2=22%, P<0.00001)]. DDL of SC was more significantly deeper than that of TC [-133.49(95% CI:-145.94 to-121.04, I^2=33%, P<0.00001)]. Other outcomes demonstrated comparable results between MC and SC.CONCLUSION: SC is more favorable at halting the progression of keratoconus, but visual acuity improvement showed comparable results between MCs and SC.

A Facile Route for the Large Scale Fabrication of Graphene Oxide Papers and Their Mechanical Enhancement by Cross-linking with Glutaraldehyde

A facile route for the large scale production of graphene oxide(GO) papers and their mechanical enhancement has been presented in this work. The novel paper-like GO made from individual GO sheets in aqueous suspension can be achieved in large scale by a simple drop casting method on hydrophobic substrates.Significant enhancement in mechanical stiffness(341%) and fracture strength(234%) of GO paper have been achieved upon modification with a small amount(less than 10 wt%) of glutaraldehyde(GA). The cross-linking reaction takes place between hydroxyl groups on the surface of GO and aldehyde groups of GA, through forming hemiacetal structure, which can result in distinct mechanical enhancement of the GO papers.

Efficacy of iontophoresis-assisted epithelium-on corneal cross-linking for keratoconus

Corneal cross-linking(CXL) is a noninvasive therapeutic procedure for keratoconus that is aimed at improving corneal biomechanical properties by induction of covalent cross-links between stromal proteins. It is accomplished by ultraviolet A(UVA) radiation of the cornea, which is first saturated with photosensitizing riboflavin. It has been shown that standard epithelium-off CXL(S-CXL) is efficacious, and it has been recommended as the standard of care procedure for keratoconus. However, epithelial removal leads to pain, transient vision loss, and a higher risk of corneal infection. To avoid these disadvantages, transepithelial CXL was developed. Recently, iontophoresis has been adopted to increase riboflavin penetration through the epithelium. Several clinical observations have demonstrated the safety and efficacy of iontophoresisassisted epithelium-on CXL(I-CXL) for keratoconus. This review aimed to provide a comprehensive summary of the published studies regarding I-CXL and a comparison between I-CXL and S-CXL. All articles used in this review were mainly retrieved from the Pub Med database. Original articles and reviews were selected if they were related to the I-CXL technique or related to the comparison between I-CXL and S-CXL.

Simultaneously enhanced moisture tolerance and defect passivation of perovskite solar cells with cross-linked grain encapsulation

The grain surfaces(film surface and grain boundary)of polycrystalline perovskite films are vulnerable sites in solar cells since they pose a high defect density and initiate the degradation of perovskite absorber.Achieving simultaneously defect passivation and grain protection from moisture is crucial for the viability of perovskite solar cells.Here,an in situ cross-linked grain encapsulation(CLGE)strategy that improves both device stability and defect passivation is reported.Cross-linkable semiconducting small molecules are mixed into the antisolvent to uniformly form a compact and conducting cross-linked layer over the grain surfaces.This cross-linked coating layer not only passivates trap states and facilitates hole extraction,but also enhances the device stability by preventing moisture diffusion.Using the CLGE strategy,a high power conversion efficiency(PCE)of 22.7%is obtained in 1.55-eV bandgap planar perovskite solar cells.The unencapsulated devices with CLGE exhibit significantly enhanced device stability again moisture and maintain>90%of their initial PCE after shelf storage under ambient condition for over10,000 h.

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.

Cross-Linked Hollow Graphitic Carbon as Low-Cost and High-Performance Anode for Potassium Ion Batteries

Large-scale and low-cost preparation of carbon-based potassium anode with long life and high capacity is one of the footstones for the development of potassium ion batteries(PIBs).Herein,a low-cost carbon-based material,cross-linked hollow graphitic carbon(HGC),is large scale synthesized to apply for PIBs anode.Its hollow structure can afford sufficient space to overcome the damage caused by the volume expansion of graphitic carbon(GC).While the cross-linked structure forms a compact interconnection network that allows electrons to rapid transfer between different GC frameworks.Electrochemical measurements demonstrated that the HGC anode exhibited low charge/discharge plateau(about 0.25 V and 0.1 V)and excellent specific capacity as high as 298 m A h g^(-1)at the current density of 50 m A g^(-1).And more important,after 200 cycles the capacity of HGC anode still shows 269 m A h g^(-1)(the decay rate of per cycle is only 0.048%).Meanwhile,the use of commercial traditional electrolyte(KPF_(6))and cheap raw materials that provide new hope for trying and realizing the large-scale production of PIBs based on carbon anode materials.

Corneal collagen cross-linking and liposomal amphotericin B combination therapy for fungal keratitis in rabbits

· AIM: To observe the therapeutic effect of corneal collagen cross-linking(CXL) in combination with liposomal amphotericin B in fungal corneal ulcers.·METHODS: New Zealand rabbits were induced fungal corneal ulcers by scratching and randomly divided into 3groups, i.e. control, treated with CXL, and combined therapy of CXL with 0.25% liposomal amphotericin B(n =5 each). The corneal lesions were documented with slit-lamp and confocal microscopy on 3, 7, 14, 21 and 28 d after treatment. The corneas were examined with transmission electron microscopy(TEM) at 4wk.·RESULTS: A rabbit corneal ulcer model of Fusarium was successfully established. The corneal epithelium defect areas in the two treatment groups were smaller than that in the control group on 3, 7, 14 and 21d(P <0.05). The corneal epithelium defect areas of the combined group was smaller than that of the CXL group(P <0.05) on 7 and 14 d, but there were no statistical differences on 3, 21 and 28 d. The corneal epithelium defects of the two treatment groups have been healed by day 21. The corneal epithelium defects of the control group were healed on 28 d. The diameters of the corneal collagen fiber bundles(42.960 ±7.383 nm in the CXL group and 37.040±4.160 nm in the combined group) were thicker than that of the control group(24.900±1.868 nm),but there was no difference between the two treatment groups. Some corneal collagen fiber bundles were distorted and with irregular arrangement, a large number of fibroblasts could be seen among them but no inflammatory cells in both treatment groups.· CONCLUSION: CXL combined with liposomal amphotericin B have beneficial effects on fungal corneal ulcers. The combined therapy could alleviate corneal inflammattions, accelerate corneal repair, and shorten the course of disease.