Cross-linkable Groups Research Articles

A Self-Matting Waterborne Polyurethane Coating for PVC Artificial Leather

A type of polyester-based self-matting waterborne polyurethane (ESMWPU) with an excellent matte effect of 0.8° and transmittance of 78.5% for PVC artificial leather was synthesized. The influence of synthesis parameters, including R value, crosslinking and hydrophilic group content, on coating gloss and transmittance was investigated. Meanwhile, the properties necessary for applying water-based resins to plasticized PVC were detailed. The results demonstrated that R value, crosslinking degree and hydrophilic group content synergistically decided the morphological changes of latex particles during their film-forming process in three aspects: particle stiffness, three-dimensional structure and particle size, respectively. With optimized parameters of R = 1.9, TMP = 2 wt% and DMPA = 1.75 wt%, ESMWPU latex particles stabilized their spherical shapes without collapsing in the film-forming process and created a rough surface, resulting in a matte effect. In terms of application performance, good wetting and adhesion for ESMWPU to a plasticized PVC surface was achieved with a 2 wt% leveling agent load. Moreover, due to the high cohesion energy of ester bonds and intermolecular hydrogen bonds, this type of polyester-based ESMWPU also depicted admirable thermal adhesion resistance. All aforementioned results distinctly demonstrate a feasible yet promising paradigm for applying ESMWPU on PVC artificial leather.

Improvement of thermal properties of polybenzoxazines synthesized from an oligonuclear phenolic compound without sacrificing toughness by introducing crosslinkable groups separated by rigid biphenyl linkers

Novel allyl-, ethynyl-, and furfuryl-containing polyfunctional benzoxazine monomers were synthesized, and the mechanical and thermal properties of their thermosets were investigated. The benzoxazines OP-ala, OP-ea, and OP-fu were successfully synthesized with high yield from an oligonuclear phenolic compound with a 4,4ʹ-dimethylenebiphenyl group as the phenol linker; paraformaldehyde; and the corresponding amines, allylamine, m-ethynylanilline, and furfurylamine, respectively, using a microwave heating technique. Despite the introduction of the crosslinkable groups, the brown polybenzoxazine films obtained via thermal curing up to 240 °C showed sufficient toughness, as shown through tensile testing. Dynamic mechanical analysis revealed that the glass transition temperature (Tg) of the thermosets considerably increase due to the introduction of the crosslinkable groups; POP-ala, POP-ea, and POP-fu films showed Tg values of 289 °C, 272 °C, and 269 °C, respectively. Moreover, thermogravimetric analysis showed that the thermal stability also increased, and the 5% weight-loss temperature of POP-ea was >430 °C.

Well-Defined pH-Sensitive Self-Assembled Triblock Copolymer-Based Crosslinked Micelles for Efficient Cancer Chemotherapy

Delivery of chemotherapeutics to cancer cells using polymeric micelles is a promising strategy for cancer treatment. However, limited stability of micelles, premature drug release and off-target effect are the major obstacles that restrict the utilization of polymeric micelles as effective drug delivery systems. In this work, we addressed these issues through the innovative design of targeted pH-sensitive crosslinked polymeric micelles for chemotherapeutic delivery. A well-defined triblock copolymer, poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate)-b-poly(butyl acrylate) (PEG-b-PHEMA-b-PBA), was synthesized by living radical polymerization, and then modified by using 4-pentenoic anhydride to incorporate pendant crosslinkable alkene groups in the middle block. The resulting copolymer underwent self-assembly in aqueous solution to form non-crosslinked micelles (NCMs). Subsequently, intramicellar thiol-ene crosslinking was performed by using 1,4-butanediol bis(3-mercaptopropionate) to give crosslinked micelles (CMs) with pH-sensitive crosslinks. The targeted CM (cRGD-DOX10-CM5) was readily prepared by using tumor-targeting ligand cyclo(Arg-Gly-Asp-D-Phe-Cys) (cRGD) together with the 1,4-butanediol bis(3-mercaptopropionate) during the crosslinking step. The study of cumulative DOX release revealed the pH-sensitive feature of drug release from these CMs. An in vitro MTT assay revealed that NCMs and CMs are biocompatible with MCF 10A cells, and the samples exhibited significant therapeutic efficiency as compared to free DOX. Cellular uptake studies confirmed higher uptake of cRGD-DOX10-CM5 by MCF 10A cancer cells via cRGD-receptor-mediated endocytosis as compared to the corresponding analogues without cRGD. These results indicate that such pH-responsive crosslinked PEG-b-PHEMA-b-PBA-based micelles are therapeutically effective against cancer cells and hold remarkable promise to act as smart drug delivery systems for cancer therapy.

Controlling the microphase morphology and performance of cross-linked highly sulfonated polyimide membranes by varying the molecular structure and volume of the hydrophobic cross-linkable diamine monomers

Morphological control is essential for tuning the performance of polymer electrolyte membranes (PEMs). Block copolymerization is an effective but complicated way to control the morphology of PEMs. It is urgent to explore a simple alternative method to achieve this target. Herein, the molecular engineering strategy that changes the molecular structure and volume of hydrophobic cross-linkable diamine and introduces a hydrophobic network structure was used to optimize the microphase morphology of sulfonated polyimides (SPIs). Three diamine monomers containing tetrafluorostyrol pendant groups have been synthesized (4-(2,3,5,6-tetrafluoro-4-vinylphenoxy)benzene-1,3-diamine (TFVPDM), 1,3-bis(2-trifluoromethyl-4-amino-phenoxy)-5-(2,3,5,6-tetrafluoro-4-vinylphenoxy)benzene (6FTFPB), 2,2-bis(3-amino-4-(2,3,5,6-tetrafluoro-4-vinylphenoxy)phenyl)hexafluoropropane (6FATFVP)). Based on these monomers, 4,4′-diaminostilbene-2,2′-disulfonic acid (DASDSA) and 1,4,5,8-naphthalenetetracarboxylicdianhydride (NTDA), three cross-linked SPIs (CSPIs: CSPI-T-10, CSPI-TP-10, CSPI-AP-10) with similar ion-exchange capacity (IEC) value of 2.29–2.46 meq. g−1 but different main-chain structures were prepared through polycondensation and thermal cross-linking process. The introduced hydrophobic cross-linked structure improves the oxidative stability and methanol resistance of CSPI membranes. The CSPI membranes prepared from cross-linkable hydrophobic diamine with larger molecular volume and containing hydrophobic structural units in the main chain exhibit more pronounced phase separation morphology and higher proton conductivity. Moreover, the methanol resistance of CSPI membranes is dependent on the combined effect of IEC, degree of crosslinking (DC), and main-chain structure. The higher DC and main-chain containing hydrophobic structure are beneficial for enhancing the methanol resistance. The CSPI-AP-10, which was prepared from the 6FATFVP with the largest molecular volume, more hydrophobic cross-linkable pendant groups and hydrophobic linkages, exhibits the best performance. The CSPI-AP-10 membranes showed high proton conductivity and excellent methanol resistance. The direct methanol fuel cells (DMFCs) assembled from CSPI-AP-10 have a high max power density (PDmax) of 106.2 mW cm−2 in 2 M methanol and 75.1 mW cm−2 in 10 M methanol. The results indicated that the CSPI-AP-10 was a promising candidate as a PEM in DMFC application.

Corneal cross-linking guards against infectious keratitis: an experimental model

BackgroundPACK-CXL (photo-activated chromophore for keratitis–corneal cross-linking) is an alternative option in treatment of corneal infections. It inhibits corneal melting by increasing the stromal resistance, besides the microbicidal effect of photo-activated riboflavin.MethodsCorneal infection with Pseudomonas aeruginosa and Staph aureus bacteria was induced in 20 eyes of 10 rabbits after 6 weeks of corneal cross-linking in half of the eyes, while the other acted as control group. Clinical and corneal histopathological examination was done to evaluate the extent of inflammation, ulceration, organism penetration, and depth of corneal stromal affection.ResultsThe control eyes developed severe inflammation compared to the cross-linked eyes. Corneal melting occurred in 6 eyes in the control versus none in cross-linked group. Histopathological examination showed that the inflammation was confined to the superficial part of the stroma with localization of the inflammation in the cross-linked eyes in contrast to the control eyes that showed deep infiltration.ConclusionPACK-CXL provides infection localization through increasing the corneal rigidity and resistance to enzymatic digestion, even in the absence of the riboflavin microbicidal role. So, early PACK-CXL is worth to be considered in the IK treatment algorithm.

Conventional versus accelerated corneal collagen cross-linking in cases of progressive keratoconus

Background Keratoconus is mainly a noninflammatory, bilateral corneal disease, which changes stability and refractive intensity. Aim Studying the visual acuity, refraction, and keratometric data of keratoconic patients who underwent either standard or accelerated cross-linking at 6-month duration. Patients and methods A randomized, comparative study with 60 eyes of 30 keratoconus patients. The study participants were categorized into two groups: A and B. Patients in group A underwent epi off conventional corneal crosslinking according to The Dresden’s protocol (3 mW/cm2 for 30 min), while patients in group B underwent epi off accelerated corneal crosslinking (30 mW/cm2 for only 3 min). Preoperative and postoperative outcomes were evaluated and then compared. Results The conventional corneal crosslinking group showed more improvement than the accelerated corneal crosslinking group in postoperative uncorrected distant visual acuity and corrected distant visual acuity at 6 months of follow-up. The two groups were similar in terms of spherical equivalent and manifest refraction. No significant change in K1 and K2 in the both groups from preoperative at 6 months. The same results were found for 6 months of f/up of corneal topography as well as central corneal thickness (CCT) and thinnest location of cornea thickness. Conclusions The study has increased the proof on the power of conventional corneal crosslinking in comparison with accelerated corneal crosslinking at 6 months of follow up.

Repeated application of riboflavin during corneal cross-linking does not improve the biomechanical stiffening effect ex vivo

PurposeTo evaluate whether repeated application of riboflavin during corneal cross-linking (CXL) has an impact on the corneal biomechanical strength in ex-vivo porcine corneas. DesignLaboratory investigation. MethodsSixty-six porcine corneas with intact epithelium were divided into three groups and analyzed. All corneas were pre-soaked with an iso-osmolar solution of 0.1% riboflavin in a phosphate-buffered saline (PBS) solution (“riboflavin solution”). Then, the corneas in Groups 1 and 2 were irradiated with a standard epi-off CXL (S-CXL) UV-A irradiation protocol (3 mW/cm2 for 30 min); while the corneas in Group 3 were not irradiated and served as control. During irradiation, Group 1 (CXL-PBS-Ribo) received repeated riboflavin solution application while corneas in Group 2 (CXL-PBS) received only repeated iso-osmolar PBS solution. Immediately after the procedure, 5-mm wide corneal strips were prepared, and elastic modulus was calculated to characterize biomechanical properties. ResultsSignificant differences in stress-strain extensiometry were found between two cross-linked groups with control group (P = 0.005 and 0.002, respectively). No significant difference was observed in the normalized stiffening effect between Groups 1 and 2 (P = 0.715). ConclusionsThe repeated application of riboflavin solution during UV-A irradiation does not affect the corneal biomechanical properties achieved with standard epi-off CXL. Riboflavin application during CXL may be omitted without altering the biomechanical stiffening induced by the procedure.

Tuning Mechanical Properties of Polymeric Hydrogels Using Orthogonally Functionalized Crosslinkers

A unique orthogonal crosslinker-induced hydrogel, whose mechanical strength can be tunable by the crosslinker topology upon thermal treatment, is described herein. The crosslinker containing cationic moieties and crosslinkable styrenyl groups was employed for the preparation of orthogonally crosslinked hydrogels having ionic and covalent characteristics. The manipulation of the orthogonal crosslinkers topology and the ionic bond strength between cationic and anionic moieties facilitated the control of the mechanical properties. Short-term temporal modulation of hydrogel moduli, a key factor of the substrates for cell development, was demonstrated and could provide dynamic microenvironment for biological process. In addition, on-demand control of the elastic properties of the hydrogels by application of a thermal stimulus provides new avenues to regulate cell growth. Furthermore, the orthogonality of the crosslinkers allowed molecular functionalization of a wide range of molecules of interest to the hydrogels by thiol-ene Michael addition (nucleophilic addition of sulfhydryl and carbon-carbon double bonds) in a friendly manner as demonstrated in our work.

Preparation and characterization of high temperature resistant thermosetting polyphenylene ether resin

AbstractTo explore high thermal properties, low dielectric constant and loss for copper clad laminates, poly(phenylene oxide) (PPE) with different end groups (allyl and epoxide groups) were successfully prepared. Firstly, low molecular weight polyphenylene ether was synthesized using the redistribution method. Then the polyphenylene ether thermosetting polymers by modifying their terminal hydroxyl groups were reported and their fundamental materials properties were compared. Through property tests and data analyses, it was found that PPE with vinyl end groups had the best performances, especially high glass transition temperature (about 230°C), the thermal conductivity was 0.32–0.38 Wm−1 K−1, low dielectric constant (about 2.5) and low dielectric loss (about 4.4 × 10−3). The possible reason was that the main chain of polyphenylene ether contains non‐polar crosslinkable group (CC). In a word, through properties comparison of thermosets of PPE, the results demonstrated that the materials of all systems were suitable for using as printed circuit boards.

Molecularly Defined Polyolefin Vitrimers from Catalytic Insertion Polymerization.

Vitrimers can combine the advantageous properties of cross-linked materials with thermoplastic processability. For the prominent case of polyethylene, established post-polymerization introduction of cross-linkable moieties results in extremely heterogeneous compositions of the chains. Here, we report the generation of functionalized polyethylenes directly by catalytic insertion polymerization, with incorporated cross-linkable aryl boronic esters or alternatively acetal-protected groups suited for cross-linking with difunctional boronic esters. In addition to the desired homogeneous in-chain distribution, the reactive cross-linkable groups are enriched at the chain ends. This enables the incorporation of all chains in the network, as also supported by simulations of all chains' compositions. The uniform molecular composition of the chains reflects in resulting vitrimers' material properties, particularly lack of leaching with solvents. At the same time, cross-linking is indeed fully reversible and the vitrimers can be recycled.

Long-term evaluation of posterior corneal surface parameters after accelerated corneal cross-linking with a comparison with uncross-linked keratoconic eyes.

To evaluate the 36months changes in posterior corneal surface parameters in keratoconic eyes after accelerated corneal cross-linking and to compare the data with uncross-linked progressive and non-progressive keratoconic eyes. Thirty five cross-linked, 30 uncross-linked progressive, and 30 uncross-linked non-progressive keratoconic eyes were included. Maximum keratometry (Kmax), thinnest pachymetry, minimum radius of curvature back (Rminback), asphericity back, posterior elevation and corneal densitometry, back corneal higher order aberrations (HOAs), back surface deviation (Db), final D, posterior radius of curvature (PRC) and 'B' unit values were recorded at baseline and at the 12, 24, 36months follow-up. Data were analyzed with repeated measures ANOVA and paired t-tests. Kmax and thinnest pachymetry were significantly changed in the cross-linked and progressive uncross-linked groups. Rminback, asphericity back, and HOAs did not change in either group. Total posterior corneal densitometry improved; posterior elevation, Db and B unit worsened in the cross-linked group and did not change in the uncross-linked groups. PRC and final D worsened in the cross-linked and progressive uncross-linked groups, and did not change in the non-progressive group. Despite a decreased Kmax, the posterior corneal surface parameters, posterior elevation values were determined to have significantly worsened in the cross-linked group and this increase was higher than in progressive uncross-linked eyes.

Tuning Polymer Hydrophilicity to Regulate Gel Mechanics and Encapsulated Cell Morphology.

Mechanically tunable hydrogels are attractive platforms for 3D cell culture, as hydrogel stiffness plays an important role in cell behavior. Traditionally, hydrogel stiffness has been controlled through altering either the polymer concentration or the stoichiometry between crosslinker reactive groups. Here, an alternative strategy based upon tuning the hydrophilicity of an elastin-like protein (ELP) is presented. ELPs undergo a phase transition that leads to protein aggregation at increasing temperatures. It is hypothesized that increasing this transition temperature through bioconjugation with azide-containing molecules of increasing hydrophilicity will allow direct control of the resulting gel stiffness by making the crosslinking groups more accessible. These azide-modified ELPs are crosslinked into hydrogels with bicyclononyne-modified hyaluronic acid (HA-BCN) using bioorthogonal, click chemistry, resulting in hydrogels with tunable storage moduli (100-1000Pa). Human mesenchymal stromal cells (hMSCs), human umbilical vein endothelial cells (HUVECs), and human neural progenitor cells (hNPCs) are all observed to alter their cell morphology when encapsulated within hydrogels of varying stiffness. Taken together, the use of protein hydrophilicity as a lever to tune hydrogel mechanical properties is demonstrated. These hydrogels have tunable moduli over a stiffness range relevant to soft tissues, support the viability of encapsulated cells, and modify cell spreading as a consequence of gel stiffness.

Outcomes of different lines of keratoconus management in a tertiary eye center in north China

To evaluate the treatment selections and outcomes of keratoconus and discuss the grading treatment of keratoconus. Medical records of 1162 patients (1863 eyes) with keratoconus treated with rigid gas permeable (RGP), corneal collagen crosslinking, and keratoplasty were reviewed. The patients were grouped according to the CLEK Study. The advanced group was further divided into a <60 D group and >60 D group. The best-corrected visual acuity (BCVA) and topographic data before and after treatment were recorded. In the 761 eyes with steep K<52 D, nonsurgical management accounted for 83.4%, while in the 735 eyes with steep K>60 D, surgical management accounted for 90.6%. A total of 618 eyes had improved BCVA at the final follow-up point (>18mo, P<0.001). When steep K was <52 D, the BCVA in the RGP group was better than those with lamellar keratoplasty (LKP; P=0.028). When steep K was >52 D, the BCVA and topographic astigmatism outcomes showed no differences among the treatment groups. When steep K was >60 D, the BCVA in eyes treated with LKP was worse than those with steep K<60 D (P=0.025). The incidence of steep K progression in the RGP group was higher in advanced group (20.0% vs 10.8%, P=0.019). The probability of future keratoplasty in RGP was higher in advanced group (14.8% vs 7.0%, P=0.027). The incidence of steep K progression in the corneal collagen crosslinking (CXL) group was higher in advanced group (32.3% vs 8.5%, P=0.007). Multivariate logistic regression revealed the following related factors for treatment options: steep K [odds ratio (OR)=1.208, 95%CI: 1.052-1.387], TA (OR=1.171, 95%CI: 1.079-1.270), and TCT (OR=0.978, 95%CI: 0.971-0.984). The level of steep K, TA, and TCT all relates to the treatment choices of both keratoplasty and non-keratoplasty, while steep K provided the highest diagnostic accuracy (AUC=0.947, P<0.001). Steep K is an important grading treatment indicator. When steep K is <52 D, RGP lenses should be recommended. It is the best time for LKP when the steep K ranges from 52 to 60 D.

Synthesis and Properties of One-Component Addition-Crosslinking Silicone Resin

A kind of MDT polysiloxane was prepared by step hydrolysis and polycondensation of alkoxysilane. It could be cured at elevated temperature with existence of microencapsulated platinum catalyst. The effects of crosslinkable groups’ contents and PhSiO1.5 content on properties of cured silicone resin were studied in detail. When the contents of crosslinkable groups were 20mol% to 30mol% and the PhSiO1.5 content was 25mol% to 30mol%, the cured silicone resin had good tensile strength, flexural strength, moderate elasticity, and low viscosity. With the increase of PhSiO1.5 content from 17mol% to 32mol%, Tg of the silicone resin could be improved by 50°C to 128°C. The thermal stability was explored by thermo gravimetric analysis. The onset temperature of thermal degradation and the center temperature of thermal degradation were 486°C and 548°C, respectively. The average dielectric constant was about 2.45 and the dielectric loss tangent value was less than 0.01. The silicone resin also showed a high-volume resistivity of 5.6×1016Ω•cm. These results suggest that such silicone resin is suitable for utilization in electronic packaging.

Repeatability and Agreement of a New Scheimpflug Device and a Hartmann-Shack Aberrometer With a Ray-Tracing Aberrometer in Normal, Keratoconus, and CXL Groups

To assess repeatability and agreement of a Scheimpflug topographer and a Hartmann-Shack aberrometer with a ray-tracing aberrometer in normal, keratoconus, and corneal cross-linking (CXL) groups. In this cross-sectional, observational study, normal, keratoconus, and CXL groups with 125 eyes in each of the three groups were included. All eyes underwent three sets of measurements, at a single visit, using the Pentacam AXL Wave (Oculus Optikgeräte GmbH) and iTrace (Tracey Technologies). Keratometry, pachymetry, objective refraction, and total ocular aberrations including root mean square (RMS) lower order aberrations (LOAs), RMS higher order aberrations (HOAs), RMS coma, and spherical aberrations (SA) were analyzed. Objective assessment of haze after CXL was done using the Pentacam AXL Wave. Repeatability was assessed using within-subject standard deviation (Sw), test-retest variability, within-subject coefficient of variation (COV), and intraclass correlation coefficient (ICC). Bland-Altman analysis assessed 95% limits of agreement and correlation coefficient (r) determined the strength of the relationship between measurements. The Pentacam AXL Wave had Sw for keratometry of 0.12 in the normal group and 0.15 in the keratoconus group and lower (poorer) Sw of 0.17 in the CXL group. For pachymetry, Sw was 9.18, 9.53, and 10.11 in the normal, keratoconus, and CXL groups, respectively. Total aberrations had ICCs ranging from 0.88 for RMS HOAs to 0.95 for SA in the normal group, 0.86 for RMS HOAs to 0.92 for SA in the keratoconus group, and 0.72 for RMS HOAs to 0.82 for SA (poorer) in the CXL group. In the normal group, mean differences between the two devices were nonsignificant for all parameters except SA (0.011 ± 0.038 μm, P < .01; limits of agreement = -0.09 to 0.07; r = 0.87). In the keratoconus group, mean differences were significant in all aberrations except RMS LOAs (-0.27 ± 0.85 μm, P = .10; limits of agreement = -3.3 to 3.8; r = 0.92). In the CXL group, all parameters varied significantly (P < .006). The Pentacam AXL Wave showed comparable repeatability in the normal and keratoconus groups, but was poorer in the CXL group, more so with increasing corneal haze. Both devices can be used interchangeably in normal eyes, except for SA, but not in eyes with keratoconus or CXL for aberration measurements. [J Refract Surg. 2022;38(3):201-208.].

Creation of a thermally cross-linkable encapsulated TADF molecule for highly efficient solution-processed hybrid white OLEDs

Robust luminogens that can be used in application for high efficiency solution-processed hybrid white organic light-emitting diodes (WOLEDs) are rarely reported. Herein, a thermally cross-linkable encapsulated thermally activated delayed fluorescence (TADF) molecule, DVCz-2CzCN, consisting of blue emissive core, encapsulation unit and thermal cross-linkable group is designed and synthesized. Systematic studies demonstrate that DVCz-2CzCN as the emitter can form a stable and uniform thin film by the solution-process, and simultaneously suppress the triplet excitons concentration quenching. Consequently, the nondoped blue solution-processed device using DVCz-2CzCN as the emissive layer exhibits blue emission with maximum external quantum efficiency (EQE) of 5.6% is achieved. Especially to solution-processed hybrid WOLED with the construction of employing the cross-linked DVCz-2CzCN as the blue-emitting component combined with an orange-emitting phosphor PO-01, exhibits a superior performance with maximum forward-viewing EQE of 14.9% and a stable Commission International de L'Eclairage (CIE) coordinate of (0.33, 0.45). This work indicates that molecular topology construction is crucial for the development of high-performance solution-processed hybrid WOLEDs. Herein, a highly efficient solution-processed hybrid white OLED was reported based on the strategy of constructing a thermally cross-linkable encapsulated TADF molecule. • Solution-processed hybrid white OLED was fabricated by utilizing a thermally cross-linkable encapsulated TADF molecule. • DVCz-2CzCN possesses good morphologic stability, sufficient solvent resistance and efficient triplet excitons confinement. • The DVCz-2CzCN-based device can afford a high blue TADF OLED by the solution-process with EQE max of 5.6%. • Solution-processed hybrid white OLED exhibits a superior performance with EQE max of 14.9%.

Injectable pH-responsive adhesive hydrogels for bone tissue engineering inspired by the underwater attachment strategy of marine mussels

A major challenge in tissue engineering is the development of alternatives to traditional bone autografts and allografts that can regenerate critical-sized bone defects. Here we present the design of injectable pH-responsive double-crosslinked adhesive hydrogels inspired by the molecular mechanism and environmental post-processing of marine mussel adhesive. Nine adhesive hydrogel formulations were developed through the conjugation of crosslinkable catechol functional groups (DOPA) and the synthetic oligomer oligo[poly(ethylene glycol) fumarate] (OPF), varying the DOPA content (w/w%) and molecular weight (MW) of the OPF backbone to produce formulations with a range of swelling ratios, porosities, and crosslink densities. DOPA incorporation altered the surface chemistry, mechanical properties, and surface topography of hydrogels, resulting in an increase in material stiffness, slower degradation, and enhanced pre-osteoblast cell attachment and proliferation. When injected within simulated bone defects, DOPA-mediated interfacial adhesive interactions also prevented the displacement of scaffolds, an effect that was maintained even after swelling within physiological conditions. Taken together, OPF-DOPA hydrogels represent a promising new material to enhanced tissue integration and the prevention of the post-implantation migration of scaffolds that can occur due to biomechanical loading in vivo.

Effect of Polymer Topology and Residue Chirality on Biodegradability of Polypeptide Hydrogels.

Polypeptide-based injectable hydrogels have attracted the attention of biomedical researchers due to their unique biocompatibility and biodegradability, tunable residue chirality, and secondary conformation of polypeptide chains. In the present study, four types of poly(ethylene glycol)-block-poly(glutamic acid)s with different topological structures and residue chirality of polypeptide segments were developed, which were grafted with tyramine side groups for further cross-linking. The results demonstrated that the covalent conjugation between the tyramine groups in the presence of horseradish peroxidase and hydrogen peroxide could form porous hydrogels rapidly. Additionally, the gelation time and mechanical strength of the hydrogels were measured. All the polymer precursors and hydrogels exhibited good cytocompatibility in vitro. Further assessment of the enzymatic degradability of the hydrogels and copolymers in vitro revealed that the degradation rate was influenced by the adjustment of polymer topology or residue chirality of polypeptide copolymers. Subsequently, the effect of copolymer topology and polypeptide chirality on in vivo biodegradability and biocompatibility was assessed. This study will provide insights into the relationship between copolymer structures and hydrogel properties and benefit future polypeptide-based hydrogel studies in biomedical applications.

Crosslinking-Induced Corneal Endothelium Dysfunction and Its Protection by Topical Ripasudil Treatment

Purpose To investigate the changes of corneal endothelium under different crosslinking conditions and the protective effect of ripasudil. Methods Corneal crosslinking groups were infiltrated with riboflavin and subsequently irradiated with 0.54 J/cm2 or 1.08 J/cm2 UVA, while noncrosslinking groups included neither UVA nor riboflavin treatment, only 1.08 J/cm2 UVA and only riboflavin treatment. Corneal opacity, variations in corneal endothelial cells, and corneal thickness of all groups were observed by slit lamp, in vivo confocal microscopy, and optical coherence tomography. Immunofluorescence staining and scanning electron microscopy were performed to evaluate changes in the structure and function of the corneal endothelium. The mice that received a corneal crosslinking dose of 1.08 J/cm2 were instilled with ripasudil to explore its protective effect on the corneal endothelium. Results Treatment with UVA and riboflavin caused an increase in corneal opacity and corneal thickness and decreased endothelial cell density. Furthermore, treatment with UVA and riboflavin caused endothelial cell DNA damage and destroyed the tight junction and pump function of the endothelium, while riboflavin or the same dose of UVA alone did not affect the endothelium. Ripasudil reduced DNA damage in endothelial cells, increased the density of cells, and protected the endothelium's integrity and function. Conclusion Riboflavin combined with UVA can damage the corneal endothelium's normal functioning. The corneal endothelium's wound healing is dose-dependent, and the ROCK inhibitor ripasudil maintains the endothelium's pump and barrier functions.

Comparing the Differences in Slowing Myopia Progression by Riboflavin/Ultraviolet A Scleral Cross-linking before and after Lens-induced Myopia in Guinea Pigs

ABSTRACT Purpose To compare the effectiveness and differences in slowing myopia progression in Guinea pigs by riboflavin/ultraviolet A (UVA) scleral cross-linking (sCXL) before and after lens-induced myopia (LIM). Methods Forty 4-week-old Guinea pigs were randomly divided into four groups (n = 10 per group): CXL-A, CXL-B, LIM, and Control groups. The right eyes in CXL-A, CXL-B, LIM groups were treated with −10.00 D lenses from 4 to 10-week old and the left eyes were untreated. In CXL-A and CXL-B groups, riboflavin/UVA sCXL was performed on the right eyes at 4 weeks and 8 weeks of age, respectively. Both eyes were untreated in Control group. The intraocular pressure (IOP), the axial length (AXL), and the refraction were measured in vivo at 4, 8, and 10 weeks of age. At 10 weeks of age, the right eyes were enucleated for the tensile test and transmission electron microscopy observations. Results The myopia has been successfully induced in LIM and CXL-B groups during 4–8 weeks. In CXL-A group, the growth rate of AXL and myopic refraction was markedly inhibited during 4–8 weeks and the inhibitory effects diminished during 8–10 weeks. During 8–10 weeks, the growth rate of AXL and myopic refraction in CXL-B were marked suppressed. At 10 weeks of age, the myopia refraction was lower and the AXL was shorter in CXL-A group in comparison to CXL-B group. The IOP was not significantly different among the 4 groups of eyes at 4, 8, and 10 weeks of age. The scleral stiffness, the fibril diameters, and the fibril density of the sclera were significantly increased in CXL-A and CXL-B groups compared to LIM group. Conclusion Riboflavin/UVA sCXL administrated before and after the myopia modeling could both slow the myopia progression in Guinea pigs. The before-myopia preventative sCXL showed lower myopic refraction in the same age comparison between the cross-linked groups. The effect of riboflavin/UVA sCXL might reduce over time and the long-term effect should be further investigated. This sCXL intervention might control the ultrastructure alterations of the sclera during the myopia remodeling.