Metal-Enhanced Helical Chirality of Coil Macromolecules: Bioinspired by Metal Coordination-Induced Protein Folding.

Although the supramolecular helical structures of biomacromolecules have been studied, the examples of supramolecular systems that are assembled using coils to form helical polymer chains are still limited. Inspired by enhanced helical chirality at the supramolecular level in metal coordination-induced protein folding, a series of alanine-based coil copolymers (poly-(l-co-d)-ala-NH2) carrying (l)- and (d)-alanine pendants were synthesized as a fresh research model to study the cooperative processes between homochirality property and metal coordination. The complexes of poly-(l-co-d)-ala-NH2 and metal ions underwent a coil-to-helix transition and exhibited remarkable nonlinear effects based on the enantiomeric excess of the monomer unit in the copolymers, affording enhanced helical chirality compared to poly-(l-co-d)-ala-NH2. More importantly, the synergistic effect of amplification of asymmetry and metal coordination triggered the formation of a helical molecular orbital on the polymer backbone via the coordination with the d orbital of copper ions. Thus, the helical chirality enhancement degree of poly-(l-co-d)-ala-NH2/Cu2+ complexes (31.4) is approximately 3 times higher than that of poly-(l-co-d)-ala-NH2/Ag+ complexes (9.8). This study not only provides important mechanistic insights into the enhancement of helical chirality for self-assembly but also establishes a new strategy for studying the homochiral amplification of asymmetry in biological supramolecular systems.

Basic Amino Acid-Modified Lignin-Based Biomass Adjuvants: Synthesis, Emulsifying Activity, Ultraviolet Protection, and Controlled Release of Avermectin.

Avermectin (AVM) is a highly effective and safe biopesticide but is very sensitive to ultraviolet (UV) light and exhibits poor water solubility. Developing green and multifunctional adjuvants is important for the protection and controlled release of AVM. In this work, a number of water-soluble enzymatic hydrolysis lignins (W-EHLs) were prepared via grafting basic amino acids and used as emulsifiers with co-surfactants to prepare high-internal phase emulsions (HIPEs). The results showed that W-EHLs with co-surfactants could be prepared with HIPEs that contained 90 vol % green oil phases such as turpentine, and the stability of the HIPEs first increased and then decreased when the rate of grafting of basic amino acids on lignin increased from 0.26 to 1.46 mmol/g. The more polar oil droplets were less deformable due to their higher viscosity, thereby affording a stability advantage to HIPEs. Subsequently, the relations between the stability and interfacial viscoelasticity of the emulsion were effectively correlated by interfacial rheology, droplet size, and physical stability tests. The results showed that HIPEs with smaller droplets had poor fluidity and strong interfacial viscoelasticity due to their higher droplet packing density, which resulted in good macroscopic stability. Like the AVM carrier, the retention rate of AVM in HIPEs was 80.1% after UV radiation for 72 h, which represented the highest UV protection efficiency in AVM delivery systems. The release curves showed that the rate of release of AVM from HIPEs was adjusted by controlling the pH value of the medium. In addition, the release of HIPEs is completely in accord with both diffusion and the matrix erosion mechanism. The strategy could be extended to other sensitive pesticides and used to promote the development of sustainable agriculture.

Synthesis and characterization of a broad-spectrum TiO2@lignin UV-protection agent with high antioxidant and emulsifying activity.

TiO2 with biocompatibility and low price was limited application in cosmetics due to its narrow UV protection range, producing free radicals under UV irradiation to accelerated skin aging and whitish. Herein, a series of highly effective broad-spectrum TiO2@lignin sunscreen microscopes (TWLx) were prepared by modulating van der Waals forces and hydrogen bonding interactions between TiO2 and lignin. The results showed that the UV main absorption peak of TWLx increased from UVA to UVA + UVB. TWLx could completely eliminate the hydroxyl radical produced by TiO2 under UV irradiation owe to introduction of lignin. Meanwhile, the combination of TiO2 and lignin could neutralize color, which made TWLx color closer to human skin. The UV-protection test showed that the SPF value of sunscreen containing 3 wt% TWLx reached 137.4. The antioxidant experiment showed that TWLx has about 16 times the DPPH radical scavenging ability of TiO2. Finally, high internal phase Pickering emulsions were prepared by using TWLx as a stabilizer. It was found that the internal phase volume fraction of the emulsion was up to 86 vol%, which could be recognized as the highest internal phase reported in suntan lotion. This work would provide new ideas for the synthesis of highly effective broad-spectrum sunscreens.

Fabrication of flower-like Ag/lignin composites and application in antibacterial fabrics.

The bacterial infection and its transmission pose a great threat to life and health, which leads to the urgent development of efficient and broad-spectrum antibacterial agents. Herein, Ag/lignin layered nanoflower (Ag/EHL-CM-0.05) was synthesized by using biomass lignin as reducing and capping agents and silver nitrate as precursor. The study showed that the size distribution of Ag NPs was uniform distribution and about 20-40 nm. The crystal surface of Ag NPs was Ag (111) surface. The minimum inhibitory concentration of Ag/EHL-CM-0.05 against E. coli and S. aureus was all 7.8 µg/mL, which was the lowest of other Ag/lignin antibacterial materials and reached a level nearly as polycationic antibacterial agents. The antibacterial mechanism suggested that Ag/EHL-CM-0.05 could release OH and Ag+, which could cause bacterial death. Finally, Ag/EHL-CM-0.05 was sprayed onto the viscose fabrics by liquid-phase spray deposition method. It was found that the inhibition zone diameter of modified viscose fabrics against E. coli and S. aureus only dropped about 0.16 cm on average after friction treatment and 0.32 cm on average after washing treatment. This work provides a new idea for the design and synthesize of efficient, broad-spectrum, and bio-compatible antibacterial agents, which has important social, economic, and environmental significance.

Curcumin-loaded high internal phase emulsions stabilized with lysine modified lignin: a biological agent with high photothermal protection and antibacterial properties.

Bacterial infections and multidrug resistance can seriously endanger the health and lives of humans, therefore the development of novel and efficient antibacterial strategies and drugs is urgently needed. Herein, a series of highly biocompatible lysine modified enzymatic hydrolysis lignins (EHL-Lys-x) were synthesized using the Mannich reaction. The sterilizing efficiency of EHL-Lys-2.0 against S. aureus and E. coli at 20 mg mL-1 is 93% and 50%, respectively, which is 26% higher than pure EHL. Quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM) analysis showed that the adsorption and adhesive force between EHL-Lys-x and bacteria increase with the increased amount of grafting of Lys on EHL owing to the increase of the electrostatic interaction between the EHL-Lys-x and bacteria, which results in an improvement in the antimicrobial activity of EHL-Lys-x. Subsequently, EHL-Lys-x combined with alkyl polyglucoside (APG) was used to stabilize the high internal phase emulsion containing curcumin (HIPEs-cur). The dispersed phase fraction of HIPE-cur is 87 vol%, which is the highest internal phase reported to date in the medical research area. The highest residual levels of curcumin in HIPEs are 60-fold, 3-fold and 5-fold compared to that in bulk oil after treatment with UV radiation, thermal emittance and after storage, respectively. The minimum inhibitory concentrations of HIPEs-cur against S. aureus and E. coli were found to be 1.56 and 6.25 mg mL-1, respectively, which are far higher than that of pure EHL-Lys-x. This strategy not only increases the chemical stability and bioavailability of curcumin, but also provides a novel method for the application of lignin in biomedical science.

One-step synthesis of versatile magnetic nanoparticles for efficiently removing emulsified oil droplets and cationic and anionic heavy metal ions from the aqueous environment.

Versatile polyethyleneimine (PEI)-coated Fe3O4 magnetic nanoparticles (MNPs) have been synthesized by a one-step solvothermal method. The morphologies, structures, and properties of MNPs prepared for different reaction times have been characterized through various techniques. The synthesized MNPs were then used to separate emulsified oil and cationic and anionic heavy metal ions from the aqueous environment; moreover, the effects of the temperature, pH, and ionic strength of aqueous media, the solvothermal reaction time, and the number of reuse cycles on the removal efficiency have been investigated in detail. The results showed that pseudo-second-order kinetics and the Langmuir isotherm well described the adsorption processes of Cu(II) and Cr(VI). The Langmuir model yielded maximum adsorption capacities of 66.6 mg g-1 for Cu(II) and 54.5 mg g-1 for Cr(VI) at pH 5.0 and 25 °C. The synthetic MNPs could also efficiently separate diesel oil or olive oil droplets stabilized by sodium dodecyl sulfate from aqueous media. Moreover, these MNPs could be recycled five times without showing significant loss in separation efficiency. Notably, the synthesized PEI-coated MNPs could simultaneously separate emulsified oil and cationic and anionic heavy metal ions from multicomponent wastewater. Such versatile PEI-coated MNPs displayed good affinity towards emulsified oil and cationic and anionic heavy metal ions, showing great potential for practical applications in the treatment of complicated industrial wastewater matrices. Graphical abstract Simultaneous separation of emulsified oil and cationic and anionic heavy metal ions from aqueous media by using polyethyleneimine-coated Fe3O4 magnetic nanoparticles.