Biomacromolecules最新文献

The use of biodegradable materials in bone plates offers remarkable advantages; however, their application in bone fixation is limited by their brittleness. Moreover, treatments tailored to patient conditions are needed in orthopedics. In this study, bone plates were fabricated with stereocomplex polylactic acid (scPLA) and the effects of poly(d-lactic acid) molecular weight and scPLA blending ratios were analyzed. Although modulus values of poly(l-lactic acid) (PLLA) and scPLA were similar, strain resistance improved at higher scPLA proportions. The enhanced elongation was owing to the presence of tie molecules within the scPLA as opposed to single PLA chains. The fabricated scPLA bone plates exhibited improved mechanical properties and transparency in the optical and near-infrared ranges. scPLA was characterized by a smaller crystallite size. These properties of scPLA combined with its biocompatibility indicate potential for various diagnostic and therapeutic orthopedic applications. Comparisons with commercial PLLA-based bone plates show no significant differences in in vivo bone-healing ability.

PET-RAFT polymerization enables precise polymer synthesis, yet conventional systems require an excess chain transfer agent (CTA) over unbound photocatalysts (PCs). Herein, a self-catalyzed strategy employing polymerizable porphyrin MTPPZnH as a dual-functional PC effectively embeds high photosensitizer content into glycopolymers for photodynamic therapy (PDT). Three galactose-bearing monomers (acrylate, methacrylate, 4-vinylbenzoate) were polymerized via PET-RAFT under optimized light conditions, achieving satisfactory M_n and relatively narrow Đ. Mechanistic studies revealed that photoexcited MTPPZnH transfers electrons/energy to CTA via a PET process, initiating polymerization, with DMSO enhancing oxygen depletion. Water-soluble glycopolymeric photosensitizers exhibited high fluorescence and singlet oxygen quantum yield. In vitro, galactose-bearing photosensitizers showed superior ASGPR-mediated endocytosis in HepG2 cells over Huh-7 and MCF-7 cells, enabling targeted PDT. The incorporation of MTPPZnH contributes to an effective multifunctional strategy, offering a promising approach for the development of high photosensitizer-embedded polymeric photosensitizers for potential PDT applications.

Skin wound healing remains challenging due to a lack of ideal wound dressings suitable for acute and chronic wounds. This study introduced a biocompatible hydrogel wound dressing, synthesized through a green chemistry approach, specifically designed to meet the dual needs of acute and chronic wound care. The innovative strategy utilized sustainable biomaterials, soy protein, and vanillin, to construct a physical–reversible chemical dual-cross-linked hydrogel exhibiting high mechanical strength, excellent adhesion, and toughness. Schiff base reversible covalent bonds enabled rapid self-healing within 10 s, significantly improving durability. In a rat liver hemorrhage model, the hydrogel rapidly sealed wounds, achieving effective hemostasis, indicating great potential for acute wound care. Furthermore, vanillin imparted the hydrogel with antimicrobial and antioxidant properties, effectively accelerating diabetic chronic wound healing. This safe and efficient advanced biobased hydrogel offers a novel perspective for wound treatment and holds significant promise for clinical applications.

Skin wound healing remains challenging due to a lack of ideal wound dressings suitable for acute and chronic wounds. This study introduced a biocompatible hydrogel wound dressing, synthesized through a green chemistry approach, specifically designed to meet the dual needs of acute and chronic wound care. The innovative strategy utilized sustainable biomaterials, soy protein, and vanillin, to construct a physical-reversible chemical dual-cross-linked hydrogel exhibiting high mechanical strength, excellent adhesion, and toughness. Schiff base reversible covalent bonds enabled rapid self-healing within 10 s, significantly improving durability. In a rat liver hemorrhage model, the hydrogel rapidly sealed wounds, achieving effective hemostasis, indicating great potential for acute wound care. Furthermore, vanillin imparted the hydrogel with antimicrobial and antioxidant properties, effectively accelerating diabetic chronic wound healing. This safe and efficient advanced biobased hydrogel offers a novel perspective for wound treatment and holds significant promise for clinical applications.

PET-RAFT polymerization enables precise polymer synthesis, yet conventional systems require an excess chain transfer agent (CTA) over unbound photocatalysts (PCs). Herein, a self-catalyzed strategy employing polymerizable porphyrin MTPPZnH as a dual-functional PC effectively embeds high photosensitizer content into glycopolymers for photodynamic therapy (PDT). Three galactose-bearing monomers (acrylate, methacrylate, 4-vinylbenzoate) were polymerized via PET-RAFT under optimized light conditions, achieving satisfactory M_n and relatively narrow Đ. Mechanistic studies revealed that photoexcited MTPPZnH transfers electrons/energy to CTA via a PET process, initiating polymerization, with DMSO enhancing oxygen depletion. Water-soluble glycopolymeric photosensitizers exhibited high fluorescence and singlet oxygen quantum yield. In vitro, galactose-bearing photosensitizers showed superior ASGPR-mediated endocytosis in HepG2 cells over Huh-7 and MCF-7 cells, enabling targeted PDT. The incorporation of MTPPZnH contributes to an effective multifunctional strategy, offering a promising approach for the development of high photosensitizer-embedded polymeric photosensitizers for potential PDT applications.

Inactivated whole tumor cell-based vaccines (WTVs) are a promising strategy for tumor immunotherapy, but have exhibited limited antitumor effects clinically. Aiming at constructing enhanced WTVs, we developed glycopolymer-engineered WTVs (G-WTVs) using a Halo-Tag protein (HTP) fusion technique and reversible addition–fragmentation chain transfer (RAFT) polymerization. In our study, G-WTVs with varying molecular weights of glycopolymers were constructed. Compared to unmodified tumor cells, all G-WTVs effectively induced the polarization of macrophages toward the M1 phenotype and promoted the secretion of pro-inflammatory cytokines. This enhanced immune response was attributed to the improved interactions between G-WTVs and the macrophages. Among the G-WTVs, the medium molecular weight variant demonstrated the most pronounced enhancement of antitumor immune responses. Notably, the administration of optimized G-WTVs effectively inhibited the growth of B16 melanoma in mice. Our findings provide a new approach to enhance the antitumor efficacy of WTVs via cell membrane glycopolymer engineering, offering a promising strategy for tumor immunotherapy.

Inactivated whole tumor cell-based vaccines (WTVs) are a promising strategy for tumor immunotherapy, but have exhibited limited antitumor effects clinically. Aiming at constructing enhanced WTVs, we developed glycopolymer-engineered WTVs (G-WTVs) using a Halo-Tag protein (HTP) fusion technique and reversible addition-fragmentation chain transfer (RAFT) polymerization. In our study, G-WTVs with varying molecular weights of glycopolymers were constructed. Compared to unmodified tumor cells, all G-WTVs effectively induced the polarization of macrophages toward the M1 phenotype and promoted the secretion of pro-inflammatory cytokines. This enhanced immune response was attributed to the improved interactions between G-WTVs and the macrophages. Among the G-WTVs, the medium molecular weight variant demonstrated the most pronounced enhancement of antitumor immune responses. Notably, the administration of optimized G-WTVs effectively inhibited the growth of B16 melanoma in mice. Our findings provide a new approach to enhance the antitumor efficacy of WTVs via cell membrane glycopolymer engineering, offering a promising strategy for tumor immunotherapy.

Sugar beet pectin, an anionic polysaccharide, and silk fibroin, a high molecular weight protein, undergo gelation through ionic interactions and conformational changes, leading to hydrogel formation. Although many studies have focused on bulk gel systems involving polysaccharides and proteins, more research is needed to investigate their properties at the microscale level. In this context, we have developed a microgel system based on a pectin/fibroin combination and investigated its properties. We focused on two gelation mechanisms: physical cross-linking and enzymatic covalent cross-linking. The pectin/fibroin microgels were fabricated using droplet-based microfluidics, and the secondary structure, mechanical properties, and degradation profiles were investigated. Our experimental results show that the microgels exhibit an ordered β-sheet structure, a Young's modulus in the range of 10 to 20 kPa, and that degradation can be promoted using protease enzymes. Finally, the biocompatibility of the microgels is assessed using the Alamar Blue cell viability assay with human pulmonary fibroblasts (HPFs). This research presents a highly functional hybrid biomaterial produced from waste products and a structural protein, demonstrating its cell compatibility and potential in tissue engineering applications.

Sugar beet pectin, an anionic polysaccharide, and silk fibroin, a high molecular weight protein, undergo gelation through ionic interactions and conformational changes, leading to hydrogel formation. Although many studies have focused on bulk gel systems involving polysaccharides and proteins, more research is needed to investigate their properties at the microscale level. In this context, we have developed a microgel system based on a pectin/fibroin combination and investigated its properties. We focused on two gelation mechanisms: physical cross-linking and enzymatic covalent cross-linking. The pectin/fibroin microgels were fabricated using droplet-based microfluidics, and the secondary structure, mechanical properties, and degradation profiles were investigated. Our experimental results show that the microgels exhibit an ordered β-sheet structure, a Young’s modulus in the range of 10 to 20 kPa, and that degradation can be promoted using protease enzymes. Finally, the biocompatibility of the microgels is assessed using the Alamar Blue cell viability assay with human pulmonary fibroblasts (HPFs). This research presents a highly functional hybrid biomaterial produced from waste products and a structural protein, demonstrating its cell compatibility and potential in tissue engineering applications.

The intracellular delivery of protein drugs via nanocarriers offers significant potential for expanding their therapeutic applications. However, the unintended activation of innate immune responses and inflammation triggered by the carriers presents a major challenge, often compromising therapeutic efficacy. Here, we present oligoethylenimine-thioketal (OEI-TK), a reactive oxygen species-responsive cationic polymer with intrinsic anti-inflammatory properties, to overcome this challenge. OEI-TK self-assembles electrostatically with bovine serum albumin (BSA) to form stable nanoparticles (OTB NPs) with excellent encapsulation efficiency. In vitro studies confirmed that OTB NPs retained OEI-TK’s antioxidant and anti-inflammatory properties, enhanced biocompatibility, and efficiently delivered BSA into cells. Furthermore, OEI-TK facilitated the intracellular delivery of β-galactosidase while preserving its enzymatic activity, demonstrating its potential for functional protein transport. These findings highlight OEI-TK as a promising platform with dual benefits of inflammation modulation and intracellular protein delivery, holding potential for the synergistic treatment of inflammation-related diseases.