High Strength UV-Resistant Composite Film of Fe3+-Coordination Lignin/PVA.

The literature on polyvinyl alcohol (PVA) films is extensive, however, these methods often necessitate intricate synthesis processes or the addition of plasticizers to modify the strength and water solubility of the PVA material. A high-strength UV radiation-resistant composite film by chelating Fe3+ with lignin and PVA, which exhibits excellent hydrolysis resistance is developed. This composite film is prepared simply by incorporating a small amount of dealkalized lignin (APPL) and ferric chloride (FeCl3) into PVA through a straightforward composite process. During the scanning test, it is noted that the film exhibits a high density of uniformly dispersed particles, endowing it with efficient ultraviolet absorption capabilities. The infrared and anti-dissolution tests reveal that the coordination of Fe3+ with lignin imparts an outstanding hydrolysis resistance to the film, obviating the need for any extender, curing agent, acid or base. The tensile fracture strength reaches an impressive 187.81Mpa in the tensile test. UV and indicator card tests unequivocally demonstrate that the film achieves a remarkable 100% anti-UV efficiency. This Fe3+ chelated lignin/PVA composite film, with its facile preparation, environmental sustainability, high strength, and outstanding anti-ultraviolet efficiency, can be deployed across diverse applications requiring robust protection against ultraviolet radiation.

Construction of a CRISPR-Biolayer Interferometry Platform for Real-Time, Sensitive, and Specific DNA Detection.

The clustered regularly interspaced short palindromic repeats (CRISPR) technology has been widely applied for nucleic acid detection because of its high specificity. By using the highly specific and irreversible bond between HaloTag and its alkane chlorine ligand, we modified dCas9 (deactivated CRISPR/Cas9) with biotin as a biosensor to detect nucleic acids. The CRISPR biosensor was facilely prepared to adequately maintain its DNA-recognition capability. Furthermore, by coupling biolayer interferometry (BLI) with the CRISPR biosensor, a real-time, sensitive, and rapid digital system called CRISPR-BLI was established for the detection of double-stranded DNA. The CRISPR biosensor immobilised on the biolayer could recruit the target DNA onto the biosensor surface and change its optical thickness, resulting in a shift in the interference pattern and responding signal of the BLI. The CRISPR-BLI system was further applied to detect the ALP gene of Escherichia coli DH5α combined with a polymerase chain reaction, which demonstrated a linear range from 20 to 20 000 pg and a low detection limit (1.34 pg). The CRISPR-BLI system is a promising approach for rapid and sensitive detection of target DNA analytes.

Constructing antibacterial polymer nanocapsules based on pyridine quaternary ammonium salt.

Excessive use of antibiotics accelerates the development and spread of drug-resistant strains, which is a huge challenge for the field of medical health worldwide. Quaternary ammonium salt polymers are considered to be membrane-active bactericidal groups with vast potential to control bacterial infections and inhibit drug resistance. Herein, we report on the creative synthesis and characterization of novel antimicrobial polymer nanocapsules based on pyridine quaternary ammonium salt. The antimicrobial polymer nanocapsules were formed by reaction of C3 symmetrical rigid monomer 2,4,6­tris(4­pyridyl)­1,3,5­triazine (TPT) and a flexible linker 1,2­dibromoethane. The polymer nanocapsule was constructed as a cationic hollow sphere composed of a two-dimensional sheet whose main chain was formed by the pyridine quaternary ammonium salt, and a part of the bromide ion was adsorbed on the sphere. This hollow nanocapsule was characterized in detail by DLS, SEM, TEM, AFM, EDS and EA. When the cationic polymer nanocapsules are close to the Gram-negative Escherichia coli, the negatively charged phospholipid molecules in the bacterial membrane are attracted to the cationic surface and lead to rupture of cells. SEM confirmed the breakage of Escherichia coli membranes. The minimum inhibitory concentration was found to be 0.04 mg/mL, and the minimum bactericidal concentration was 0.1 mg/mL. Our experiments demonstrated that the adsorption of negatively charged phospholipid molecules on the surface of the pyridine quaternary ammonium salt polymer can kill Gram-negative bacteria without inserting quaternary ammonium salt hydrophobic groups into the cell membrane.

Template-Free Construction of Highly Ordered Monolayered Fluorescent Protein Nanosheets: A Bioinspired Artificial Light-Harvesting System.

Using biological materials for light-harvesting applications has attracted considerable attention in recent years. Such materials provide excellent environmental compatibility and often exhibit superior properties over synthetic materials. Herein, inspired by the outstanding energy transfer performance in coelenterates, we constructed a template-free, highly ordered two-dimensional light-harvesting system by covalent-induced coassembly of EBFP2 (donor) and EGFP (acceptor), in which the fluorescent chromophores were well distributed and adopted a fixed orientation. By introducing approximate square planar binding sites on the side surface of protein, assembly pattern was pin down and self-assembly extended in orthogonal directions to achieve monolayered and tessellated protein nanoarrays. The excellent antiself-quenching property of fluorescent proteins endowed the coassembled system with attractive light-harvesting capability. Even at high local concentrations, a low resonance energy transfer self-quenching was observed and, therefore, energy can be efficiently transferred. More importantly, the distance between adjacent chromophores is continuously adjustable. By making minor changes to the length of the inducing linker, we have achieved significant control over the size of the assembly. A micron-sized light-harvesting system with satisfactory energy transfer efficiency was finally obtained. This work developed a template-free light-harvesting system completely based on fluorescent proteins (FPs), which overcame the restriction of using templates. Not limited to this work, the special core-shell structure of FPs may be expected to direct the optimization of fluorescent dyes by cladding.

Reductive-Responsive, Single-Molecular-Layer Polymer Nanocapsules Prepared by Lateral-Functionalized Pillar[5]arenes for Targeting Anticancer Drug Delivery.

Herein, a new reductive-responsive pillar[5]arene-based, single-molecule-layer polymer nanocapsule is constructed for drug delivery. The functionalized system shows good biocompatibility, efficient internalization into targeted cells and obvious triggered release of entrapped drugs in a reducing environment such as cytoplasm. Besides, this smart vehicle loaded with anticancer drug shows excellent inhibition for tumor cell proliferation and exhibits low side effect on normal cells. This work not only demonstrates the development of a new reductive-responsive single molecular layer polymer nanocapsule for anticancer drug targeting delivery but also extends the design of smart materials for biomedical applications.

Yellow-Emissive Carbon Dot-Based Optical Sensing Platforms: Cell Imaging and Analytical Applications for Biocatalytic Reactions.

Carbon dots (CDs) have attracted increasing interest in bioimaging and sensing recently. Herein, we present a simple synthetic strategy to prepare yellow-emissive CDs (λem = 535 nm) by one-pot hydrothermal treatment of p-phenylenediamine and aspartic acid. The as-prepared CDs possess outstanding optical features, excellent biocompatibility, and low cytotoxicity, especially for fluorescence (FL) cellular imaging. Interestingly, by combining the quenching and recognition ability of silver nanoparticles (AgNPs) with the optical capacity of CDs, a label-free strategy for specifically monitoring H2O2-generated biocatalytic processes was proposed, such as glucose oxidase-induced conversion of glucose, cholesterol oxidase-catalyzed oxidization of cholesterol, and bienzyme of acetylcholinesterase and choline oxidase-mediated reaction of acetylcholine. In this process, AgNPs act as a "nanoquencher" to decrease the FL intensity of CDs via surface plasmon-enhanced energy-transfer mechanism. The enzymatic oxidation product (H2O2) subsequently etches the AgNPs to silver ions, thus recovering the FL of CDs, which enabled this proposed nanosensor to sensitively detect H2O2-generated biocatalytic processes. The above results pave the way to implement CDs as FL labels for biosensors and biological imaging.

Cucurbit[8]uril-Based Giant Supramolecular Vesicles: Highly Stable, Versatile Carriers for Photoresponsive and Targeted Drug Delivery.

Highly stable giant supramolecular vesicles were constructed by hierarchical self-assembly of cucurbit[8]uril (CB[8])-based supra-amphiphiles for photoresponsive and targeted intracellular drug delivery. These smart vesicles can encapsulate the model drugs with high loading efficiencies and then release them by manipulating photoswitchable CB[8] heteroternary complexation to regulate the formation and dissociation of supra-amphiphiles that cause dramatic morphological changes of the assemblies to achieve remote optically controlled drug delivery. More importantly, the confocal microscopy analysis, cellular uptake experiment, and cell viability assay have shown that the giant vesicles are able to maintain the structural integrity and stability within actual cellular environments and exhibit obvious advantages for intracellular drug delivery such as low toxicity, easy surface modification for tumor-targeting selectivity, and rapid internalization into different human cancer cell lines. A synergistic mechanism that integrates multiple pathways including energy-dependent endocytosis, macropinocytosis, cholesterol-dependent endocytosis, and microtubule-related endocytosis was determined to facilitate the internalization process. Moreover, cytotoxicity experiments and flow cytometric analysis have demonstrated that the doxorubicin hydrochloride-loaded vesicles exhibited a significant therapeutic effect for tumor cells upon UV light irradiation, which makes the photoresponsive system more promising for potential applications in pharmaceutically relevant fields.

Photocontrolled protein assembly for constructing programmed two-dimensional nanomaterials.

Precise self-assembly of proteins with structural heterogeneity, flexibility, and complexity into programmed arrays to mimic the exquisite architectures created by Nature is a great challenge for the development of protein-based functional nanomaterials. Herein, we present a strategy that integrates light stimuli and covalent coupling to prepare size-tunable two-dimensional (2D) protein nanostructures by remote photocontrol. Using Ru(bpy)3 2+ as a photosensitizer, stable protein one (SP1) was redesigned and self-assembled into nanosheets in the presence of ammonium persulfate (APS) through a rapid and efficient oxidative protein crosslinking reaction. In the design, only a serine-to-tyrosine mutation at position 98 was introduced into SP1 by combining computer simulation and genetic engineering for specific covalent coupling under white light illumination. The chemical and topographical specificities of the photosensitized crosslinking reaction allow control of the direction of protein assembly to form extended 2D nanosheets, which are packed in an orderly manner along the lateral surface of ring-shaped SP1S98Y. Notably, the growth of SP1 nanosheets exhibited isotropical characteristics and can be dynamically mediated by illumination time to achieve precise control of the size of the assembled architectures. The subsequent heat treatment further revealed the excellent thermostability of the 2D periodic SP1 nanostructures, which may find promising applications in the fabrication of various nanobiomaterials after functionalization. The present work demonstrates that the visible light-triggered crosslinking strategy is a facile and environmentally friendly method for constructing advanced protein architectures through hierarchical self-assembly.

Dynamic protein self-assembly driven by host-guest chemistry and the folding-unfolding feature of a mutually exclusive protein.

A novel exploration utilizing a well-designed fusion protein containing a redox stimuli-responsive domain was developed to construct dynamic protein self-assemblies induced by cucurbit[8]uril-based supramolecular interactions. The reversible interconversion of the morphology of the assemblies between nanowires and nanorings was regulated precisely by redox conditions.

Enzyme-Regulated Fast Self-Healing of a Pillararene-Based Hydrogel.

Self-healing, one of the exciting properties of materials, is frequently used to repair the damage of biological and artificial systems. Here we have used enzymatic catalysis approaches to develop a fast self-healing hydrogel, which has been constructed by dynamic aldimine cross-linking of pillar[5]arene-derivant and dialdehyde-functionalized PEG followed by encapsulation of glucose oxidase (GOx) and catalase (CAT). In specific, the two hydroxyl groups at terminal of PEG4000 are functionalized with benzaldehydes that can interact with amino-containing pillar[5]arene-derivant through dynamic aldimine cross-links, resulting in reversible dynamic hydrogels. Modulus analysis indicated that storage modulus (G') and loss modulus (G″) of the hydrogel increased obviously as the concentration of dialdehyde-functionalized PEG4000 (DF-PEG4000) increased or the pH values decreased. Once glucose oxidase (GOx) and catalase (CAT) are located, the hydrogel could be fast repaired, with self-healing efficiency up to 100%. Notably tensile test showed that the repair process of pillararene-based hydrogel can finish in several minutes upon enzyme catalysis, while it needed more than 24 h to achieve this recovery without enzymes. This enzyme-regulated self-healing hydrogel would hold promise for delivering drugs and for soft tissue regeneration in the future.

Enzyme-Triggered Defined Protein Nanoarrays: Efficient Light-Harvesting Systems to Mimic Chloroplasts.

The elegance and efficiency by which chloroplasts harvest solar energy and conduct energy transfer have been a source of inspiration for chemists to mimic such process. However, precise manipulation to obtain orderly arranged antenna chromophores in constructing artificial chloroplast mimics was a great challenge, especially from the structural similarity and bioaffinity standpoints. Here we reported a design strategy that combined covalent and noncovalent interactions to prepare a protein-based light-harvesting system to mimic chloroplasts. Cricoid stable protein one (SP1) was utilized as a building block model. Under enzyme-triggered covalent protein assembly, mutant SP1 with tyrosine (Tyr) residues at the designated sites can couple together to form nanostructures. Through controlling the Tyr sites on the protein surface, we can manipulate the assembly orientation to respectively generate 1D nanotubes and 2D nanosheets. The excellent stability endowed the self-assembled protein architectures with promising applications. We further integrated quantum dots (QDs) possessing optical and electronic properties with the 2D nanosheets to fabricate chloroplast mimics. By attaching different sized QDs as donor and acceptor chromophores to the negatively charged surface of SP1-based protein nanosheets via electrostatic interactions, we successfully developed an artificial light-harvesting system. The assembled protein nanosheets structurally resembled the natural thylakoids, and the QDs can achieve pronounced FRET phenomenon just like the chlorophylls. Therefore, the coassembled system was meaningful to explore the photosynthetic process in vitro, as it was designed to mimic the natural chloroplast.

Selenium-containing organic nanoparticles as silent precursors for ultra-sensitive thiol-responsive transmembrane anion transport.

An anion transporter with a selenoxide group was able to form nanoparticles in water, whose activity was fully turned off due to the aggregation effect. The formed nanoparticles have a uniform size and can be readily dispersed in water at high concentrations. Turn-on of the nanoparticles by reducing molecules is proposed to be a combined process, including the reduction of selenoxide to selenide, disassembly of the nanoparticles and location of the transporter to the lipid membrane. Accordingly, a special acceleration phase can be observed in the turn-on kinetic curves. Since turn-on of the nanoparticles is quantitatively related to the amount of reductant, the nanoparticles can be activated in a step-by-step manner. Due to the sensibility of this system to thiols, cysteine can be detected at low nanomolar concentrations. This ultra-sensitive thiol-responsive transmembrane anion transport system is quite promising in biological applications.

Enzymetically regulating the self-healing of protein hydrogels with high healing efficiency.

Enzyme-mediated self-healing of dynamic covalent bond-driven protein hydrogels was realized by the synergy of two enzymes, glucose oxidase (GOX) and catalase (CAT). The reversible covalent attachment of glutaraldehyde to lysine residues of GOX, CAT, and bovine serum albumin (BSA) led to the formation and functionalization of the self-healing protein hydrogel system. The enzyme-mediated protein hydrogels exhibit excellent self-healing properties with 100% recovery. The self-healing process was reversible and effective with an external glucose stimulus at room temperature.