Solid-state NMR of vulcanized natural rubber/butadiene rubber blends:Local organization and cross-linking heterogeneities This article is part of the virtual special issue“Solid-state NMR studies on polymers and biological solids”

Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.

Early changes in corneal densitometry after FS-LASIK combined with accelerated corneal cross-linking for correction of high myopia

AIM:To observe the effects of femtosecond laserassisted excimer laser in situ keratomileusis combined with accelerated corneal cross-linking(FS-LASIK Xtra)on corneal densitometry after correcting for high myopia.METHODS:In this prospectively study,130 patients underwent FS-LASIK or FS-LASIK Xtra for high myopia.Their right eyes were selected for inclusion in the study,of which 65 cases of 65 eyes in the FS-LASIK group,65 patients with 65 eyes in the FS-LASIK Xtra group.Patients were evaluated for corneal densitometry at 1,3,and 6mo postoperatively using Pentacam Scheimpflug imaging.RESULTS:Preoperative differences in corneal densitometry between the FS-LASIK and FS-LASIK Xtra groups in different ranges were not statistically significant(P>0.05).Layer-by-layer analysis revealed statistically significant differences in the anterior(120μm),central,and total layer corneal densitometry between the FS-LASIK and FS-LASIK Xtra groups at 1 and 3mo postoperatively(all P<0.05),the FS-LASIK Xtra group is higher than that of the FS-LASIK group.Analysis of different diameter ranges showed statistically significant differences between the FS-LASIK group and the FS-LASIK Xtra group at 1mo postoperatively in the ranges of 0–2,2–6,and 6–10 mm(both P<0.05);At 3mo postoperatively,the FS-LASIK Xtra group is higher than that of the FS-LASIK group in the ranges of 0–2 and 2–6 mm(P<0.05).At 6mo postoperatively,there were no statistically significant differences in corneal densitometry between the FS-LASIK group and the FS-LASIK Xtra group in different diameter ranges(all P>0.05).CONCLUSION:There is an increase in internal corneal densitometry during the early postoperative period after FS-LASIK Xtra for correction of high myopia.However,the densitometry values decreased to the level of conventional FS-LASIK at 6mo after surgery,with the most significant changes observed in the superficial central zone.

A novel analysis of Scheimpflug total corneal refractive power following corneal cross-linking in mild to moderate keratoconus

AIM:To detect an earlier improvement in mild to moderate keratoconus following corneal cross-linking(CXL)with total corneal refractive power(TCRP)using ray tracing method.METHODS:A total of 40 eyes of 30 consecutive patients who underwent CXL for progressive keratoconus were retrospectively enrolled.The following keratometric parameters provided by Pentacam HR,including maximum keratometry(Kmax),steepest keratometry(Ksteep),3 mm zonal TCRP centered over corneal apex(TCRPapex,zone 3 mm),zonal mean keratometry and TCRP centered over corneal cone(Kmcone,zone and TCRPcone,zone 1,2,3 mm)were evaluated preoperatively and 1,3,6,and 12 mo postoperatively.Groups 1 and 2 were defined based on Kmax at postoperative 1 mo as improved(the initial improvement group)or worsen(the initial deterioration group)compared to the preoperative level.RESULTS:In the overall group,only keratometric parameters based on ray tracing method displayed significant improvement early at 3 mo postoperatively,in which TCRPcone,zone 1 mm and 2 mm exhibited the largest flattening(0.57 D and 0.53 D,respectively).In Group 1,only Kmax,Kmcone,zone 2 mm and TCRPcone,zone 2 mm showed significant improvement initially at 1 mo postoperatively,in which Kmax exhibited the largest improvement(1.05 D),followed by TCRPcone,zone 2 mm(0.82 D).In Group 2,only keratometric parameters based on ray tracing method and Kmcone,zone 3 mm showed slight but not significant improvement early at 3 mo,in which TCRPcone,zone 3 mm displayed the most improvement(0.19 D),followed by TCRPcone,zone 2 mm(0.15 D).CONCLUSION:The findings indicate that a 2 mm zonal TCRP centered over Kmax could earlier detect keratometric improvement by CXL compared to other commonly used parameters in mild to moderate keratoconic eyes.

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 investig...

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.

Radiation-induced cross-linking:a novel avenue to permanent 3D modification of polymeric membranes

Membrane fouling is always the biggest problem in the practice of membrane separation technologies,which strongly impacts their applicability,separation efficiency,cost effectiveness,and service lifespan.Herein,a simple but effective 3D modification approach was designed for permanently functionalizing polymeric membranes by directly cross-linking polyvinyl alcohol(PVA)under gamma-ray irradiation at room temperature without any additives.After the modification,a PVA layer was constructed on the membrane surface and the pore inner surface of polyvinylidene fluoride(PVDF)membranes.This endowed them with good hydrophilicity,low adsorption of protein model foulants,and easy recoverability properties.In addition,the pore size and distribution were customized by controlling the PVA concentration,which enhanced the rejection ability of the resultant membranes and converted them from microfiltration to ultrafiltration.The crosslinked PVA layer was equipped with the resultant membranes with good resistance to chemical cleaning by acidic,alkaline,and oxidative reagents,which could greatly prolong the membrane service lifetime.Furthermore,this approach was demonstrated as a universal method to modify PVDF membranes with other hydrophilic macromolecular modifiers,including polyethylene glycol,sodium alginate,and polyvinyl pyrrolidone.This modification of the membranes effectively endowed them with good hydrophilicity and antifouling properties,as expected.

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.

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,I2=75%,P=0.03）;TC vs SC 1.15（95%CI：0.54-1.75,I2=50%,P=0.0002）].SE decreased significantly for SC when compared to AC[0.62（95%CI：0.38-0.86,I2=22%,P〈0.00001）].DDL of SC was more significantly deeper than that of TC[-133.49（95%CI：-145.94 to-121.04,I2=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.

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.

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.

Comparison of corneal biological parameters between transepithelial and epithelium-off corneal cross-linking in keratoconus

AIM:To evaluate the differences in corneal biological parameters between transepithelial and epithelium-off corneal cross-linking in keratoconus.METHODS:In our prospective clinical trial,40 patients(60 eyes)with progressive keratoconus were randomized to undergo corneal cross-linking with transepithelial(TE group,n=30)or epithelium-off(EO group,n=30)keratoconus.Examinations comprised topography,corneal biomechanical analysis and specular microscopy at 6 mo postoperatively.RESULTS:The keratometer values were not significantly different between the TE and EO corneal cross-linked groups in different periods(each P>0.05).The corneal thickness of the EO group was greater than that of the TE group at 1 wk after the operation(each P<0.05).Regarding corneal biomechanical responses,the EO group showed a longer second applanation length than TE group(P=0.003).Regarding the corneal endothelial function,standard deviation of the endothelial cell size,and coefficient of variation in the cell area,the values of EO group were larger than those of TE group at 1 wk(P=0.011,0.026),and the percentage of hexagonal cells in EO group was lower than that in TE group at 1 and 6 mo(P=0.018,0.019).CONCLUSION:Epithelium-off corneal cross-linking may strengthen corneal biomechanics better than TE procedure can.However,the TE procedure with a lower ultraviolet-A irradiation intensity would be safer for corneal endothelial function.

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.

fFabrication of three-dimensional proteinaceous micro- and nano-structures by femtosecond laser cross-linking

Proteins are a class of biomaterials having a vast array of functions, including the catalysis of metabolic reactions, DNA replication, stimuli response and transportation of molecules. Recent progress in laser-based fabrication technologies has enabled the formation of three-dimensional （3D） proteinaceous micro- and nano-structures by femtosecond laser cross-linking, which has expanded the possible applications of proteins. This article reviews the current knowledge andrecent advancements in the femtosecond laser cross-linking of proteins. An overview of previous studies related to fabri-cation using a variety of proteins and detailed discussions of the associated mechanisms are provided. In addition, ad-vances and applications utilizing specific protein functions are introduced. This review thus provides a valuable summaryof the 3D micro- and nano-fabrication of proteins for biological and medical applications.

Study of Sorption Properties of Anion Exchangers with Long-Chained Cross-Linking Agents for Tungsten Hydrometallurgy

The macroporous anion exchangers with long-chained cross-linking agents were investigated for the tungsten recovery from salt solutions.The physical-chemical characteristics of these sorbents were studied by means of sorption-desorption experiment aswell as electron and IR-spectroscopy.The anion exchangers on the basis of macroporous copolymers of methylacrylate and divinyl-ester of diethyleneglycol or tetravinyl-ester of pentaerythritol possess the exchange capacity to tungsten 2--5 times greater than the porous anion exchangers on the basis of styrene and divinylbenzene,therefore they can be used for selective tungsten recovery from comulex salt solutions.

Photo-induced Alignment Behavior of Azobenzene-containing Polymer Films with Different Cross-linking Degree

Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree （from 0 to 32%, which was monitored by FT-IR spectra measurement）. Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated ＂writing＂ and ＂erasing＂ cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.

Investigation of the efficiency of intrastromal ring segments with cross-linking using different sequence and timing for keratoconus

· AIM: To evaluate and compare the efficacy and stability of intrastromal corneal ring segment(ICRs)implantation with cross-linking(CXL) using different sequence and timing.· METHODS: In this single retrospective study, 86 keratoconic eyes subjected the ICRs implantation. We analyzed only 41 eyes that had complete follow-ups.They were divided into three groups: ICRs implantation was applied only(group normal), ICRs first followed by CXL immediately(group CXL-S), CXL first followed by ICRs long after(group CXL-B). The visual acuity,refractive results, keratometry were compared preoperatively and 1y postoperatively. Their differences among the three groups were also analyzed.·RESULTS: Group normal comprised 25 eyes, group CXL-S 8 eyes, and group CXL-B 8 eyes. There were improvements in the mean uncorrected distance visual acuity(UDVA) and the mean corrected distance visual acuity(CDVA) compared preoperatively and 1y postoperatively [UDVA: 0.31(P =0.030) logarithmic minimum angle of resolution(log MAR) group normal, 0.4(P =0.020) group CXL-S, 0.45(P =0.001) group CXL-B;CDVA : 0. 21 log MAR( P = 0. 013) group normal, 0. 30(P =0.036) group CXL-S; 0.26(P =0.000) group CXL-B].The refractive and topographic outcomes also showed improvements. In terms of comparisons among the three groups, all the P values were above 0.05, showing no significant difference. But only group CXL-B had improvement in UDVA and CDVA for all the patients.·CONCLUSION: With safety and good visual outcomes,ICRs implantation is a viable alternative for keratoconus.No significant difference was found among these three groups.

Inhibiting effect of[HOEmim][BF_4]and[Amim]Cl ionic liquids on the cross-linking reaction of bituminous coal

In order to reduce the hazard of coal spontaneous combustion,the cross-linking reaction between O-containing functional groups of coal should be inhibited.So the inhibitory effect of an ionic liquid(IL) on the cross-linking reaction was studied.The O-containing functional groups change the weight loss and H_2O,CO_2,CO yields of bituminous coal before and after[H0Emim][BF_4]and[Amim]Cl pre-treatment and were detected by Fourier Transform Infrared spectroscopy(FT1R) and Thermo Gravimetric(TC) analysis.The results show that | AmimjCI has a weaker ability to inhibit the cross-linking reaction of bituminous coal compared to[HOEmim][BF_4].Besides,based on Quantum Chemistry calculation,it was found that the different inhibiting effects of |H0Emim][BF_4]and[Amim]Cl are greatly related to their anions and the H linked with C2 atom on the imidazole ring.The H-donor ability of coal will be enhanced by[HOEmim][BF_4]leading to a weaker cross-linking reaction of coal.

Synthesis and Applications of Tetra- functional Branched Poly(ethylene glycol) Derivative for the Decellularized Valve Leaflets Cross-linking

To investigate the effects of polyethylene glycol cross-linking on the mechanical properties, 80 porcine aortic valves were harvested, decellularized, and introduced with sulflaydryl. Then the valves were randomly assigned into 5 experimental groups and 1 control group （n=16）. For the valves in those experimental groups, branched polyethylene glycol diacrylate （PEG） of 5 different molecular weights （3.4, 8, 12, 20, 40 kDa） were synthesized and cross-linked with them respectively. The efficiency of the cross-linking was determined by measuring the amount of residual thiol group and the mechanical properties of the cross-linked valve leaflets were assessed by uni-axial planar tensile testing. The efficiency of the PEG 20 kDa group was 70.72±2.33%, obviously superior to that of the other groups （p〈0.05）. Tensile test proved that branched PEG cross-linking can significantly enhance the mechanical behaviors of the deeellularized valve leaflet and the Young＇s modulus of each group was positively correlated with the molecular weight of PEG. It was concluded that branched PEG with the molecular weight of 20 kDa can effectively cross-link the decellularized porcine aortic valves and improve their mechanical properties, which makes it a promising cross-linker that can be used in the modification of decellularized tissue engineering valves.

Study on Various Compositions of Polyvinyl Alcohol and Starch Blends by Cross-Linking with Glyoxal

The aim of this study is to analyze the various compositions of polyvinyl alcohol (PVA) and starch blends. The blends have been cross-linked with glyoxal to enhance its properties. The hydroxyl groups of PVA and starch react with glyoxal via formation of acetal bonds;hence crosslinking could take place. The cross-linking of glyoxal is observed in various analytical methods such as DSC and FTIR. The cross-linked blends showed better thermal and mechanical properties. Viscosity, tensile shear strength, pencil hardness and ultimate stress were evaluated to estimate the changes due to cross-linking. It was observed that the cross-linking is directly proportional to starch, since the starch hydroxyl groups are easily accessible for reacting. The cross-linked blend showed better cohesion between its chains, thereby increasing glass transition temperature. It was reflected in the subsequent increase in tensile strength properties.

Effect of Cross-linking Agent on Barbituric Acid-initiated Resin

To improve the tensile bond strength of denim bonding agents, the adhesion between denim and MMA resin was investigated by applying initiator systems containing 1-cyclohexyl-5-ethyl barbituric acid (CEB), copper acetyl acetonate (CAA), quaternary ammonium chloride (QAC). cupric ion, with the addition of TEGDMA, an.d pretreatment solution for denim, and an HEMA primer. The effects of a cross-linking agent on barbituric acid-initiated denim bonding resin were examined by measuring degree of conversion, molecular weight, hardness of bonding resin, and tensile bond strengths.