A stimuli-responsive multiple chirality switching material, which can regulate opposed chiral absorption characteristics, has great application value in the fields of optical modulation, information storage and encryption, etc. However, due to the rareness of effective functional systems and the complexity of material structures, developing this type of material remains an insurmountable challenge. Herein, a smart polymer film with multiple chirality inversion properties was fabricated efficiently based on a newly-designed acid & base-sensitive dye-grafted helical polymer. Benefited from the cooperative effects of various weak interactions (hydrogen bonds, electrostatic interaction, etc.) under the aggregated state, this polymer film exhibited a promising acid & base-driven multiple chirality inversion property containing record switchable chiral states (up to five while the solution showed three-state switching) and good reversibility. The creative exploration of such a multiple chirality switching material can not only promote the application progress of current chiroptical regulation technology, but also provide a significant guidance for the design and synthesis of future smart chiroptical switching materials and devices.

Lipid nanoparticles (LNPs) coated with functional and biocompatible polymers have been widely used as carriers to deliver oligonucleotide and messenger RNA therapeutics to treat diseases. Poly(ethylene glycol) (PEG) is a representative material used for the surface coating, but the PEG surface-coated LNPs often have reduced cellular uptake efficiency and pharmacological activity. Here, we demonstrate the effect of pH-responsive ethylenediamine-based polycarboxybetaines with different molecular weights as an alternative structural component to PEG for the coating of LNPs. We found that appropriate tuning of the molecular weight around polycarboxybetaine-modified LNP, which incorporated small interfering RNA, could enhance the cellular uptake and membrane fusion potential in cancerous pH condition, thereby facilitating the gene silencing effect. This study demonstrates the importance of the design and molecular length of polymers on the LNP surface to provide effective drug delivery to cancer cells.
The study presents the unique characteristics of small interfering RNA (siRNA)-loaded lipid nanoparticles (LNPs) with different lengths of PGlu(DET-Car), revealing the length of PGlu(DET-Car) critically affects the formation of a stable LNP, the cellular uptake, membrane fusion, and gene silencing abilities.

A major challenge in using nanocarriers for intracellular drug delivery is their restricted capacity to escape from endosomes into the cytosol. Here, we significantly enhance the drug delivery efficiency by accurately predicting and regulating the transition pH (pH0) of peptides to modulate their endosomal escape capability. Moreover, by inverting the chirality of the peptide carriers, we could further enhance their ability to deliver nucleic acid drugs as well as antitumor drugs. The resulting peptide carriers exhibit versatility in transfecting various cell types with a high efficiency of up to 90% by using siRNA, pDNA, and mRNA. In vivo antitumor experiments demonstrate a tumor growth inhibition of 83.4% using the peptide. This research offers a potent method for the rapid development of peptide vectors with exceptional transfection efficiencies for diverse pathophysiological indications.

Encapsulation of plant polyphenols with micro-/nano-carriers for enhanced bioavailability has been well documented, but the preparation of these carriers and subsequent loading of polyphenols is a multiple process, which is generally complicated with potentially unexpected negative effects on the bioactivity of the polyphenols. Here, we reported a convenient method to assemble carrier-free polyphenol nanoparticles (NPs) based on oxidative coupling polymerization. The effectiveness was assessed with five different polyphenols including pyrocatechol (PY), catechin (CA), epigallocatechin gallate (EGCG), tannic acid (TA), and proanthocyanidin (PC). The structural characteristics of these assembled nanoparticles (PY NPs, CA NPs, EG NPs, TA NPs, and PC NPs) were systematically analyzed with dynamic light scattering (DLS), transmission electron microscopy (TEM), UV-visible spectroscopy, and Fourier transform infrared spectroscopy (FTIR). All NPs were colloidally stable with varying NaCl concentrations from 0 to 300 mM, were acid-resistant and alkali-intolerant, and were suitable for oral administration. An array of antioxidant assays further confirmed the superior antioxidant capabilities of NPs over Trolox and polyphenol monomers, indicating that the oxidative polymerization of polyphenols did not compromise the polyphenol activity of NPs. The in vitro simulated digestion studies validated that these responsive NPs were actually gastrointestinal pH-responsive and applicable to the gastrointestinal physiological environment. The bioaccessibility assessments by using a static in vitro digestion model revealed that better results were achieved with NPs than polyphenol monomers, with TA NPs showing about 1.5-fold higher bioaccessibility than other polyphenol nanoparticles. The present study with five polyphenols demonstrated that the oxidative polymerization of polyphenols provides an effective platform to assemble various carrier-free NPs with enhanced antioxidant activity, favorable stability, and improved bioaccessibility, which could be used promisingly as a functional food ingredient in food matrices or as oral drug delivery candidates for helping to manage human health or treating various gastrointestinal disorders in both the pharmaceutical and nutritional fields.

Polymer-based pH-responsive fluorescent materials have the characteristics of fast response, real-time monitoring, visualisation, and easy forming. Consequently, they have attracted widespread attention in wound healing, sweat monitoring, security and anti-counterfeiting, freshness detection of aquatic products, metal-ion sensing and bioimaging. This paper analyses the preparation principles and characteristics of pH-responsive fluorescent materials based on cellulose, chitosan and proteins. It then outlines the fluorescence properties, environmental response mechanisms and applications of various luminescent materials. Next, the research indicates that amines, N-heterocyclic rings, carboxyl groups and amino plasmonic groups on the fluorescent molecule structure and polymer skeleton appear to change the degree of ionisation under acid or alkali stimulation, which affects the light absorption ability of chromophore electrons, thus producing fluorescence changes in fluorescent materials under different pH stimuli. On this basis, the challenges and growth encountered in the development of proteins and polysaccharides-based pH-responsive fluorescent materials were prospected to provide theoretical references and technical support for constructing pH-responsive fluorescent materials with high stability, high sensitivity, long-lasting pH-response and wide detection range.

Multivalent ion cross-linking has been used to form hydrogels between sodium alginate (SA) and hyaluronic acid (HA) in previous studies. However, more stable and robust covalent cross-linking is rarely reported. Herein, we present a facile approach to fabricate a SA and HA hydrogel for wound dressings with injectable, good biocompatibility, and high ductility. HA was first reacted with ethylenediamine to graft an amino group. Then, it was cross-linked with oxidized SA with dialdehyde to form hydrogel networks. The dressing can effectively promote cell migration and wound healing. To increase the antibacterial property of the dressing, we successfully loaded tetracycline hydrochloride into the hydrogel as a model drug. The drug can be released slowly in the alkaline environment of chronic wounds, and the hydrogel releases drugs again in the more acidic environment with wound healing, achieving a long-term antibacterial effect. In addition, one-dimensional partial differential equations based on Fickian diffusion with time-varying diffusion coefficients and hydrogel thicknesses were used to model the entire complex drug release process and to predict drug release.

Smart hydrogels have shown great potential applications in disease treatment due to their controlled and local drug-release ability. Herein, a smart hydrogel with pH-responsive, injectable, and self-healing properties for controlled release of taxifolin (TFL) was prepared by freezing-thawing and photo-crosslinking methods. The crosslinking network of hydrogels (CS-CA hydrogels) was constructed by the hydrogen bonds, Schiff base bonds, and cyclobutane rings using chitosan (CS) and coumarin (CA) as raw materials. The CS-CA hydrogel demonstrated a compressive strength of 1.04 MPa, a self-healing efficiency of 99.9 %, and could maintain structural and functional integrity after injection. In addition, the drug release rate and shape of the CS-CA hydrogels were tunable due to its pH sensitivity. The TFL cumulative release reached 60 % within 12 h at pH = 4, and after equilibration, the cumulative release of TFL at pH = 4 (80 %) was significantly higher than at pH = 9.2 (50 %). The CCK8 experiment showed that the resulting hydrogel had no cytotoxicity. Meanwhile, subcutaneous implantation experiments in mice showed that the CS-CA hydrogels had favorable biodegradability and compatibility.

Wound infection has become a healthy economic burden globally. Current wound management mainly relies on the use of antibiotics; however, the misuse and overuse of antibiotics can easily result in antibiotic resistance. This study proposes a biodegradable, biocompatible, and pH-responsive amphiphilic 11-aminoundecanoic acid-grafted polysuccinimide (AUA-PSI) as a nanocarrier for drug encapsulation via nanoprecipitation. The succinimide groups in the backbone of PSI allow facile postfunctionalization via an aminolysis reaction. The degree of substitution of AUA can be modulated to adjust the degradation rate, pH sensitivity, and drug-release profile. Antibiotic rifampicin was incorporated with AUA-PSI to form Rif-AUA-PSI nanoparticles and demonstrated pH-responsiveness and antimicrobial activity. Because of the elevation of the pH value from pH = ∼ 5.5 in healthy skin to pH > 7 in an infected wound, Rif-AUA-PSI nanoparticles begin to decompose and release Rif upon the hydrolysis of succinimide/amide and deprotonation of carboxyl groups. The effective suppression of bacterial growth by Rif-AUA-PSI nanoparticles was demonstrated using a plate count method. More importantly, Rif-AUA-PSI nanoparticles were physically deposited on cotton gauze bandages as an antibiotic wound dressing. The Rif-AUA-PSI-modified gauze was applied to infected wounds on rats for wound management. The results show fast wound healing and inhibition of bacterial growth, which demonstrate that the method promotes modulable amphiphilicity, biodegradability, biocompatibility, pH-responsiveness, and facile modification for nanomedicine and medical devices.

Chitosan-pectin emulsion-filled hydrogel (EFH) was developed to enhance the bioaccessibility of lipophilic bioactive compounds through intestinal delivery. The EFH, incorporating a sodium caseinate-stabilized emulsion, was prepared using cold-set gelation under acidic conditions without crosslinking agents. Increasing the pectin concentration (0.75-1.50%, w/v) improved the mechanical strength and compactness of the EFH. The pH-responsive EFH retained the emulsion at pH 2.0 and released it at pH 7.4. In vitro digestion demonstrated that the EFH remained intact during oral and gastric stages, while the emulsion alone became destabilized. During intestinal digestion, the release of free fatty acids from the EFH decreased from 58.67% to 43.76% as the pectin concentration increased from 0.75% to 1.50%. EFH with 0.75% and 1.00% pectin significantly improved curcumin bioaccessibility compared to the emulsion alone. These findings demonstrate the potential of chitosan-pectin EFH as a novel carrier system for enhancing the bioaccessibility of lipophilic bioactive compounds.

In this work, a novel biomass-based aerogel, polydopamine decorated pomelo peel powder/polyethyleneimine/κ-carrageenan (PPEKC) aerogel, was developed for dye wastewater treatment. The as-prepared PPEKC aerogel possessed a robust structure and good compressible resilience. As expected, this aerogel presented remarkable efficacy in eliminating both anionic and cationic dyes. The experimental maximum adsorption capacities were 2016.7 mg g-1 for congo red (CR) at pH = 5 and 1176.6 mg g-1 for methylene blue (MEB) at pH = 11, following with ultra-fast adsorption rates. The adsorption kinetics followed the pseudo-second-order model. The adsorption isotherms exhibited a stronger alignment with the Langmuir isotherm model for CR at 308 K and MEB at 288, 298, 308 K. The Freundlich isotherm model yielded a suitable fit for the adsorption of CR at 288 and 298 K. Thermodynamic analyses indicated that the removal of CR and MEB was spontaneous and endothermic. The adsorption mechanisms involved electrostatic interactions, π-π interactions, and hydrogen bonds. Intriguingly, it could achieve bidirectional selective adsorption of anionic and cationic dyes in the designed pH values, due to pH-tunable surface charge. Additionally, it also exhibited favorable reusability and antibacterial activity. Therefore, the as-prepared PPEKC aerogel could be a promising biosorbent for dye wastewater treatment.