Tunicate-inspired polyallylamine-based hydrogels for wet adhesion: A comparative study of catechol- and gallol-functionalities.

HYPOTHESIS: Functional adhesives with excellent adhesive strength in wet as well as dry environments are actively studied for various applications. In particular, the adhesion mechanism of marine organisms has been imitated to achieve strong adhesion in wet environments. EXPERIMENTS: Polyallylamine (PAA) was modified with catechol groups (CA), which mimic the mussel adhesion proteins, and gallol groups (GA) found in tunicates to compare the gelation, self-healing, and adhesive properties of the modified polymers according to pH change. The effect of the Schiff base formation and antioxidant capacity exerted by polyphenolic groups were investigated by comparing the self-healing behaviors of the two hydrogels. Furthermore, the wet adhesion and antibacterial properties of the PAA-CA and PAA-GA hydrogels were evaluated in terms of the synergistic effects of the amino groups and catechol or gallol groups. FINDINGS: The self-crosslinkable PAA-CA and PAA-GA hydrogels showed high self-healing ability owing to these dynamic imine bonds. Furthermore, the PAA-based hydrogels showed higher adhesive strength in wet environments than in dry environments owing to the synergism between the catechol or gallol groups and amino groups. Overall, the PAA-GA hydrogels are superior to the PAA-CA ones, indicating that gallol-functionalized hydrogels have great potential as multifunctional adhesives.

Bioinspired Self-Healable Polyallylamine-Based Hydrogels for Wet Adhesion: Synergistic Contributions of Catechol-Amino Functionalities and Nanosilicate.

Recently, many studies have been reported on functional adhesives that are applicable in wet conditions as well as in air conditions. In this study, a novel polymer hydrogel that mimics the mussel foot proteins (Mfps) was designed as an adhesive that can adhere strongly to various substrates in wet conditions. Polyallylamine-hydrocaffeic acid (PAA-CA) conjugates were synthesized to introduce the catechol moiety into the PAA backbone. The PAA-CA hydrogels were simply prepared by controlling the pH to enable the formation of a dynamic imine bond via the Schiff base reaction without any additional cross-linking agents. Owing to its residual amino groups, the PAA-CA hydrogel showed improved adhesive strength in wet conditions, which was found to be ∼4.7 times higher than in dry conditions. In addition, dual-cross-linked PAA-CA hydrogels were prepared by the addition of laponite (LP). The synergistic effect of the dynamic imine bonds and ionic bonds of the PAA-CA/LP nanocomposite hydrogels led to improved mechanical and self-healing properties. PAA-based hydrogels have great potential for more diverse applications than those of the commercial adhesives.

Mussel-inspired poly(γ-gl utamic acid)/nanosilicate composite hydrogels with enhanced mechanical properties, tissue adhesive properties, and skin tissue regeneration.

It was demonstrated herein that the adhesive property of catechol-functionalized nanocomposite hydrogel can be enhanced by tuning the cohesive strength due to the secondary crosslinking between catechol and synthetic bioactive nanosilicate, viz. Laponite (LP). The nanocomposite hydrogel consists of the natural anionic poly(γ-glutamic acid) (γ-PGA), which was functionalized with catechol moiety, and incorporated with disk-structured LP. The dual-crosslinked hydrogel was fabricated by enzymatic chemical crosslinking of catechol in the presence of horseradish peroxidase (HRP) and H2O2, and physical crosslinking between γ-PGA-catechol conjugate and LP. The PGADA/LP nanocomposite hydrogels with catechol moieties showed strong adhesiveness to various tissue layers and demonstrated an excellent hemostatic properties. These PGADA/LP nanocomposite hydrogels are potentially applied for injectable tissue engineering hydrogels, tissue adhesives, and hemostatic materials. STATEMENT OF SIGNIFICANCE: Recently, many attempts have been performed to manufacture high-performance tissue adhesives using synthetic and natural polymer-based materials. In order to apply in various biological substrates, commercially available tissue adhesives should have an improved adhesive property in wet conditions. Here, we designed a mussel-inspired dual crosslinked tissue adhesive that meets most of conditions as an ideal tissue adhesive. The designed tissue adhesive is composed of poly(γ-glutamic acid)-dopamine conjugate (PGADA)-gluing macromer, horseradish peroxidase (HRP)/hydrogen peroxide (H2O2)-enzymatic crosslinker, and Laponite (LP)-additional physical crosslinking nanomaterial. The PGADA hydrogel has tunable physicochemical properties by controlling the LP concentration. Furthermore, this dual crosslinked hydrogel shows strong tissue adhesive property, regardless of the tissue types. Specially the PGADA hydrogel has tissue adhesive strength four times higher than commercial bioadhesive. This dual crosslinked PGADA hydrogel with improved tissue adhesion property is a promising biological tissue adhesive for various tissue type in surgical operation.

Enzymatically Cross-Linked Poly(γ-glutamic acid) Hydrogel with Enhanced Tissue Adhesive Property.

Enzymatic cross-linking of polymer-catechol conjugates in the presence of horseradish peroxidase (HRP) and H2O2 has emerged as an important method to fabricate in situ-forming, injectable hydrogels. Subsequently, tissue adhesion studies using catechol-containing polymers were extensively reported. However, because of the presence of numerous variables such as polymer concentration, oxidizing agent/enzyme, and stoichiometry, the design of the polymer with optimized tissue adhesive property is still challenging. In this study, a poly(γ-glutamic acid) (γ-PGA)-dopamine (PGADA) conjugate was synthesized, and in situ hydrogels were fabricated via enzymatic cross-linking of a catechol moiety. To optimize the tissue adhesive property of the PGADA hydrogel, the effect of various factors, such as polymer concentration, catechol substitution degree (DS), HRP concentration, and H2O2 content, on the gelation behavior and mechanical strength was investigated. The gelation behavior of PGADA hydrogels was characterized using a rheometer and rotational viscometer. Also, the possibility of its use as a tissue adhesive was examined by evaluating the tissue adhesion strength in vitro and ex vivo.

Influence of smoking on blood cadmium concentration in university students.

OBJECTIVES: This study was performed to examine the influence of smoking on the blood cadmium concentration in university students. METHODS: The study included 300 university students. A questionnaire interview was used to collect data. The urine cotinine and blood cadmium levels were measured as biological exposure indices. The data were analyzed using t-tests ANOVA and ANCOVA. RESULTS: The median value of blood cadmium concentration was equal in both males and females (0.8microgram/liter). This level was relatively low in comparison with the reference value suggested by WHO (2001). ANCOVA showed that smoking related variables, urine cotinine and smoking amount, were significantly associated with the blood cadmium level (P=0.004, 0.015). However, the values with regard to traffic related air pollution were not significantly associated with the blood cadmium level. CONCLUSIONS: Smoking is an important source of nonoccupational cadmium exposure in young people. The Blood cadmium level is at least 10% higher in active smokers than in passive or nonsmokers. The level of urine cotinine can be used as an indicator of non-occupational exposure of respirable cadmium due to smoking, as there is a good correlation bestween smoking amount and the urine cotinine level.