In Situ Reduction of Silver Nanoparticles/Urushiol-Based Polybenzoxazine Composite Coatings with Enhanced Antimicrobial and Antifouling Performances.

Marine anti-fouling coatings represent an efficient approach to prevent and control the marine biofouling. However, a significant amount of antifouling agent is added to improve the static antifouling performance of the coatings, which leads to an issue whereby static antifouling performance conflicts with eco-friendly traits. Herein, this work reports an in situ reduction synthesis of silver nanoparticles (AgNPs) within polymers to produce composite coatings, aiming to solve the aforementioned issue. Firstly, urushiol-based benzoxazine monomers were synthesized by the Mannich reaction, using an eco-friendly natural product urushiol and n-octylamine and paraformaldehyde as the reactants. Additionally, AgNPs were obtained through the employment of free radicals formed by phenolic hydroxyl groups in the urushiol-based benzoxazine monomers, achieved by the in situ reduction of silver nitrate in benzoxazine. Then, the urushiol-based benzoxazine/AgNPs composite coatings were prepared by the thermosetting method. AgNPs exhibit broad-spectrum and highly efficient antimicrobial properties, with a low risk to human health and a minimal environmental impact. The composite coating containing a small amount of AgNPs (≤1 wt%) exhibits effective inhibition against various types of bacteria and marine microalgae in static immersion, thereby displaying outstanding antifouling properties. This organic polymer and inorganic nanoparticle composite marine antifouling coating, with its simple preparation method and eco-friendliness, presents an effective solution to the conflict between static antifouling effectiveness and environmental sustainability in marine antifouling coatings.

Designed Synthesis of Fe/Zr Bimetallic Organic Framework to Enhance the Selective Conversion of H2S to Sulfur.

The development of stable and effective catalysts to convert toxic H2S into high value-added sulfur is essential for production safety and environmental protection. However, the inherent defects of traditional iron- and zirconium-based catalysts, such as poor activity, high oxygen consumption, and low sulfur selectivity, limit their further developments and applications. Herein, the Fe-Zr bimetallic organic framework FeUIO-66(x) with different cubic morphologies was synthesized via a facile solvothermal method. The results indicate that the introduction of Fe not only increases the specific surface area and weak L-sites of the catalyst without changing its crystal structure, which provides enough reaction space and more active sites for the adsorption and activation of H2S, but also reduces the activation energy of the reaction, significantly promoting the selective oxidation of H2S. As a result, the as-obtained FeUIO-66(1) catalyst exhibits the highest desulfurization activity and superior durability and water resistance stability, and its H2S conversion and sulfur selectivity within 50 h are 100 and 88%, respectively. More importantly, the structure of the catalyst after the desulfurization reaction is consistent with that of the fresh counterpart. The study offers new insights into the development of effective and stable bimetallic catalysts to eliminate H2S and recycle sulfur.

Sustainable Coating Based on Zwitterionic Functionalized Polyurushiol with Antifouling and Antibacterial Properties.

Zwitterionic polymer coatings facilitate the formation of hydration layers via electrostatic interactions on their surfaces and have demonstrated efficacy in preventing biofouling. They have emerged as a promising class of marine antifouling materials. However, designing multifunctional, environmentally friendly, and natural products-derived zwitterionic polymer coatings that simultaneously resist biofouling, inhibit protein adhesion, exhibit strong antibacterial properties, and reduce algal adhesion is a significant challenge. This study employed two diisocyanates as crosslinkers and natural urushiol and ethanolamine as raw materials. The coupling reaction of diisocyanates with hydroxyl groups was employed to synthesize urushiol-based precursors. Subsequently, sulfobetaine moieties were introduced into the urushiol-based precursors, developing two environmentally friendly and high-performance zwitterionic-functionalized polyurushiol antifouling coatings, denoted as HUDM-SB and IPUDM-SB. The sulfobetaine-functionalized polyurushiol coating exhibited significantly enhanced hydrophilicity, with the static water contact angle reduced to less than 60°, and demonstrated excellent resistance to protein adhesion. IPUDM-SB exhibited antibacterial efficacy up to 99.9% against common Gram-negative bacteria (E. coli and V. alginolyticus) and Gram-positive bacteria (S. aureus and Bacillus. sp.). HUDM-SB achieved antibacterial efficacy exceeding 95.0% against four bacterial species. Furthermore, the sulfobetaine moieties on the surfaces of the IPUDM-SB and HUDM-SB coatings effectively inhibited the growth and reproduction of algal cells by preventing microalgae adhesion. This zwitterionic-functionalized polyurushiol coating does not contain antifouling agents, making it a green, environmentally friendly, and high-performance biomaterial-based solution for marine antifouling.

Tannic Acid-Induced Gelation of Aqueous Suspensions of Cellulose Nanocrystals.

Nanocellulose hydrogels are a crucial category of soft biomaterials with versatile applications in tissue engineering, artificial extracellular matrices, and drug-delivery systems. In the present work, a simple and novel method, involving the self-assembly of cellulose nanocrystals (CNCs) induced by tannic acid (TA), was developed to construct a stable hydrogel (SH-CNC/TA) with oriented porous network structures. The gelation process is driven by the H-bonding interaction between the hydroxyl groups of CNCs and the catechol groups of TA, as substantiated by the atoms in molecules topology analysis and FTIR spectra. Interestingly, the assembled hydrogels exhibited a tunable hierarchical porous structure and mechanical moduli by varying the mass ratio of CNCs to TA. Furthermore, these hydrogels also demonstrate rapid self-healing ability due to the dynamic nature of the H-bond. Additionally, the structural stability of the SH-CNC/TA hydrogel could be further enhanced and adjusted by introducing coordination bonding between metal cations and TA. This H-bonding driven self-assembly method may promote the development of smart cellulose hydrogels with unique microstructures and properties for biomedical and other applications.

Ultrastrong and Tough Urushiol-Based Ionic Conductive Double Network Hydrogels as Flexible Strain Sensors.

Ionic conductive hydrogels have attracted increasing research interest in flexible electronics. However, the limited resilience and poor fatigue resistance of current ionic hydrogels significantly restrict their practical application. Herein, an urushiol-based ionic conductive double network hydrogel (PU/PVA-Li) was developed by one-pot thermal initiation polymerization assisted with freeze-thaw cycling and subsequent LiCl soaking. Such a PU/PVA-Li hydrogel comprises a primary network of covalently crosslinked polyurushiol (PU) and a secondary network formed by physically crosslinked poly(vinyl alcohol) (PVA) through crystalline regions. The obtained PU/PVA-Li hydrogel demonstrates exceptional mechanical properties, including ultrahigh strength (up to 3.4 MPa), remarkable toughness (up to 1868.6 kJ/m3), and outstanding fatigue resistance, which can be attributed to the synergistic effect of the interpenetrating network structure and dynamic physical interactions between PU and PVA chains. Moreover, the incorporation of LiCl into the hydrogels induces polymer chain contraction via ionic coordination, further enhancing their mechanical strength and resilience, which also impart exceptional ionic conductivity (2.62 mS/m) to the hydrogels. Based on these excellent characteristics of PU/PVA-Li hydrogel, a high-performance flexible strain sensor is developed, which exhibits high sensitivity, excellent stability, and reliability. This PU/PVA-Li hydrogel sensor can be effectively utilized as a wearable electronic device for monitoring various human joint movements. This PU/PVA-Li hydrogel sensor could also demonstrate its great potential in information encryption and decryption through Morse code. This work provides a facile strategy for designing versatile, ultrastrong, and tough ionic conductive hydrogels using sustainable natural extracts and biocompatible polymers. The developed hydrogels hold great potential as promising candidate materials for future flexible intelligent electronics.

Urushiol-Based Benzoxazine Containing Sulfobetaine Groups for Sustainable Marine Antifouling Applications.

Benzoxazine resins are new thermosetting resins with excellent thermal stability, mechanical properties, and a flexible molecular design, demonstrating promise for applications in marine antifouling coatings. However, designing a multifunctional green benzoxazine resin-derived antifouling coating that combines resistance to biological protein adhesion, a high antibacterial rate, and low algal adhesion is still challenging. In this study, a high-performance coating with a low environmental impact was synthesized using urushiol-based benzoxazine containing tertiary amines as the precursor, and a sulfobetaine moiety into the benzoxazine group was introduced. This sulfobetaine-functionalized urushiol-based polybenzoxazine coating (poly(U-ea/sb)) was capable of clearly killing marine biofouling bacteria adhered to the coating surface and significantly resisting protein attachment. poly(U-ea/sb) exhibited an antibacterial rate of 99.99% against common Gram negative bacteria (e.g., Escherichia coli and Vibrio alginolyticus) and Gram positive bacteria (e.g., Staphylococcus aureus and Bacillus sp.), with >99% its algal inhibition activity, and it effectively prevented microbial adherence. Here, a dual-function crosslinkable zwitterionic polymer, which used an "offensive-defensive" tactic to improve the antifouling characteristics of the coating was presented. This simple, economic, and feasible strategy provides new ideas for the development of green marine antifouling coating materials with excellent performance.

Metal Ion-Catalyzed Low-Temperature Curing of Urushiol-Based Polybenzoxazine.

In this work, urushiol-based polybenzoxazine is cured by the Lewis acid (FeCl3, AlCl3, and CuCl2) at low temperature instead of high thermal curing temperature. The effect of the Lewis acid on structures and properties of the polymers is revealed. The relating urushiol-based benzoxazine monomer (BZ) was synthesized by natural urushiol, formaldehyde, and n-octylamine. The monomer was reacted with the Lewis acid with a molar ratio of 6:1 (Nmonomer: NMetal) at 80°C to obtain films that can be cured at room temperature. The chemical structures of benzoxazine monomers were identified by Fourier-transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). The interaction between the metal ion and the polymers is revealed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance-FTIR (ATR-FTIR). The effect of the Lewis acid on the mechanical properties, wettability, and thermal stability was investigated. The results show that the benzoxazine cured by Cu2+ has a better performance than that cured by Al3+ and Fe3+.

Two-dimensional lamellar polyimide/cardanol-based benzoxazine copper polymer composite coatings with excellent anti-corrosion performance.

The economic loss and environmental damage caused by metal corrosion is irreversible. Thus, effective methods, such as coating technologies are used to protect metal surfaces from corrosion. In this work, cardanol-based benzoxazine (CB) was synthesized by a solvent-free method using cardanol, paraformaldehyde and n-octylamine. A cardanol-based benzoxazine copper polymer (CBCP) with good mechanical properties was then prepared by CuCl2 catalysis and can be cured at room temperature. Subsequently, polyimide corrosion inhibitors with a two-dimensional sheet structure (pyromellitic dianhydride polyimide (PDPI) and 1,4,5,8-naphthalene tetracarboxylic dianhydride polyimide (NDPI)) were designed and prepared. Lastly, PDPI or NDPI was mixed with CBCP to obtain two-dimensional lamellar polyimide/cardanol-based benzoxazine copper polymer composite coatings. The Tafel curves and electrochemical impedance spectroscopy (EIS) measurements showed composite coatings with good corrosion resistance in different corrosive media. Compared to CBCP coating, the anticorrosion performance of the composite coatings improved obviously, especially the coating obtained with 0.5 wt% PDPI. It exhibits a high polarization resistance (3.874 × 109 Ω), a high protection efficiency (99.99% and 97.98%) and low corrosion rate (3.376 × 10-6 mm year-1). This work suggested a facile and eco-friendly strategy for preparing bio-based anticorrosive composite coatings from low cost and abundant cardanol and polyimide corrosion inhibitors, which will significantly promote their application in metal anticorrosion.

Bimetallic Metal-Organic Frameworks MIL-53(xAl-yFe) as Efficient Catalysts for H2S Selective Oxidation.

Catalytic oxidation of H2S is a crucial green pathway that can fully convert H2S into value-added elemental S for commercial use. However, achieving high catalytic stability and S selectivity by traditional-metal-based catalysts still remain a major challenge. Herein, a facile one-step solvothermal strategy is designed for the fabrication of bimetallic MIL-53(xAl-yFe) catalysts. The as-synthesized MIL-53(1Al-5Fe) possesses ample coordinatively unsaturated metal sites, which served as efficient catalytic sites for the selective oxidation of H2S. As a result, the representative MIL-53(1Al-5Fe) achieves a S yield of nearly 100% at 100-160 °C with almost no obvious decrease of catalytic stability in the run of 30 h. Under the defined reaction conditions, the bimetallic metal-organic frameworks are obviously superior to MIL-53(Al) (49.3%) and MIL-53(Fe) (70.5%) in S yield. This study suggests that the introduction of elemental Al into MIL-53(xAl-yFe) could effectively modulate the electronic properties and spatial configuration of the catalysts, further conducing the adsorption and activation of H2S and thus accelerating the dissociation of H2S into a key intermediate S* and improving their catalytic performance.

Facile one-pot synthesis of silver nanoparticles encapsulated in natural polymeric urushiol for marine antifouling.

Silver nanoparticle-based coatings have been regarded as promising candidates for marine antifouling. However, current toxic fabrication methods also lead to environment risks. Nanoparticle agglomeration, poor compatibility with polymer, and rapid release of Ag+ result in short-term efficacy. In this study, a facile one-pot synthesis method of silver nanoparticles (AgNPs) encapsulated in polymeric urushiol (PUL) was developed. AgNPs were synthesized in situ by natural urushiol, serving as a reductant, dispersant and surfactant. Simultaneously, silver nitrate catalyzed the polymerization of urushiol into PUL. This in situ reduction method made AgNPs uniformly distributed in the polymer matrix. The binding between the AgNPs and the PUL resulted in the stable release of Ag+. Results showed the antibacterial rate of a 0.1% AgNPs coating is 100% in laboratory experiments. This environment-friendly coating showed good microbial inhibition performance with long-term (120 days) marine antifouling efficacy. This study shows the potential of preparing an eco-friendly coating with long-term marine antifouling ability.

Correction: Facile one-pot synthesis of silver nanoparticles encapsulated in natural polymeric urushiol for marine antifouling.

[This corrects the article DOI: 10.1039/D0RA02205E.].

Effect of Silane on the Active Aging Resistance and Anticorrosive Behaviors of Natural Lacquer.

Environmentally friendly and renewable hybrid lacquer coatings with excellent aging resistant and anticorrosion properties were studied. The coatings were prepared using raw lacquer coupled with the silane agent 3-aminopropyltriethoxysilane or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane via an eco-friendly sol-gel preparation process. The physical-mechanical properties, thermal stability, aging resistance, and anticorrosion properties of the as-prepared coatings were analyzed. Additionally, the surface of the coatings before and after an accelerated aging treatment was studied by scanning electron microscopy and X-ray photoelectron spectroscopy. The results revealed that the hybrid lacquer coating A (with a raw lacquer-to-APTES mass ratio of 1.8:1) resulted in films with a significantly enhanced antiaging effect (e.g., six times higher than that of lacquer at a gloss loss rate of 30%). Besides, this film revealed an exceptional anticorrosion performance (with the lowest corrosion current I corr = 2.476 × 10-10 A·cm-2) and a high protection efficiency (99.99 and 94.10%), as demonstrated by its electrochemical characteristics. Furthermore, all films exhibited a good barrier because of their dense structure, which prevents the corrosive medium from penetrating the coating during the salt spray test analysis after 1000 h. And the coating A relatively layered was distributing any significant cancaves, integrity better than all coatings studied, indicating that the based electrolyte was easier to penetrate it after salt spraying 2000 h.

[Surface characterization of urushiol-titanium chelate polymers by inverse gas chromatography].

Urushiol-titanium chelate polymer (UTP), the reaction product of urushiol with titanium compound, is a special eco-friendly polymer with excellent performances, such as strong acids-resistance, strong alkalis-resistance, salt solution-resistance and several organic solvent-resistance. Inverse gas chromatography (IGC) was used to measure the dispersive component of surface free energy (gamma(s)d) and the Lewis acid-base parameters of UTP in this work. The gamma(s)d and the acid/base characters of UTP' surfaces were estimated by the retention time with different non-polar and polar probes at infinite dilution region. n-Pentane (C5), n-hexane (C6), n-heptane (C7), n-octane (C8) and n-nonane (C9) were chosen as the non-polar probes to characterize the gamma(s)d. Trichloromethane (CHCl3), tetrahydrofuran (THF) and acetone were chosen as polar probes to detect the Lewis acid-base parameters. The specific free energy (deltaG(a)AB) and the enthalpy (deltaH(a)AB) of adsorption corresponding to acid-base surface interactions were determined. By correlating deltaH(a)AB with the donor and acceptor numbers of the probes, the acidic (K(a)) and the basic (K(b)) parameters of the samples were calculated. The results showed that the dispersive components of the free energy of UTP were 37.68, 33.53, 35.92, 24.01 and 31.32 mJ/m2 at 70, 80, 90, 100 and 110 degrees C, respectively. The Lewis acidic number K(a) of UTP was 0.185 3, and the Lewis basic number K(b) was 0.966 2. The results were of great importance to the study of the surface properties and the applications for urushiol-metal chelate polymers.

On the UV-induced polymeric behavior of Chinese lacquer.

To dry Chinese lacquer rapidly for the protection and restoration of archeological findings coated by lacquer or excavated lacquer wares and the development of new application of this lacquer, we carried out UV curing technology to improve its curing rate using a high-pressure mercury lamp as a UV source in the absence of any additional photoinitiator. The effects of mainly specific components in Chinese lacquer sap and the role of each reactive group of urushiol, namely hydroxyl groups, hydrogen on the phenyl ring, and olefins in the side chain, in the course of UV exposure were well-investigated. The UV-cured Chinese lacquer films were also characterized by FT-IR, (1)H NMR, SEM, TGA, and Py-GC/MS. The results showed that urushiol was the main component to form Chinese lacquer films, and decomposed to generate the urushiol semiquinone radicals, which sequentially induced the polymerization of Chinese lacquer by radical polymerization, as well as radical substitution under UV irradiation. In addition, the TG analysis suggested that polysaccharide and glycoproteins were integrated with the UV-cured films by covalent bonding. Furthermore, this method could be suitable to fast cure other phenol bearing long aliphatic unsaturated chain, such as CNSL.