Biomacromolecules最新文献

Composite biomaterials with excellent biocompatibility and biodegradability are crucial in tissue engineering. In this work, a composite protein and polysaccharide photo-cross-linkable hydrogel was prepared using silk fibroin methacrylate (SFMA) and hyaluronic acid methacrylate (HAMA). SFMA was obtained by the methacrylation of degummed SF with glycidyl methacrylate (GMA), while HA was methacrylated by 2-aminoethyl methacrylate hydrochloride (AEMA). We investigated the effect of the addition of 1 wt % HAMA to 5, 10, and 20 wt % SFMA, which resulted in an increase in both static and cycling mechanical strengths. All composite hydrogels gelled under UV light in <30 s, allowing for rapid stabilization and stiffness increases. The biocompatibility of the hydrogels was confirmed by direct and indirect contact methods and by evaluation against the NIH3T3 and MC3T3 cell lines with a live-dead assay by confocal imaging. The range of obtained mechanical properties from developed composite and UV-cross-linkable hydrogels sets the basis as possible future biomaterials for various biomedical applications.

Molecularly imprinted polymers (MIPs) are a class of synthetic recognition materials that offer a cost-effective and robust alternative to antibodies. While MIPs have found predominant use in biosensing and diagnostic applications, their potential for alternative uses, such as enzyme inhibition, remains unexplored. In this work, we synthesized a range of acrylamide-based hydrogel MIP microparticles (35 μm) specific for the recognition of α-amylase. These MIPs also showed good selectivity toward the target protein with over 96% binding of the target protein, compared with the control nonimprinted polymer (NIP) counterparts. Specificity of the MIPs was determined with the binding of nontarget proteins, trypsin, human serum albumin (HSA), and bovine serum albumin (BSA). The MIPs were further evaluated for their ability to inhibit α-amylase enzymatic activity, showing a significant decrease in activity. These findings highlight the potential of MIPs as enzyme inhibitors, suggesting an innovative application beyond their conventional use.

Materials from renewable carbon feedstock can limit our dependence on fossil carbon and facilitate the transition from linear carbon-intensive economies to sustainable, circular economies. Chitin nanofibrils (ChNFs) isolated from white mushrooms offer remarkable environmental benefits over conventional crustacean-derived nanochitin. Herein, ChNFs are utilized to reinforce polymers of natural and fossil origin, carboxymethyl cellulose (CMC) and polyvinylpyrrolidone (PVP), respectively. Incorporation of 5 wt % ChNFs increases the Young's modulus from 1217 ± 11 to 1509 ± 22 MPa for PVP and from 1979 ± 48 to 2216 ± 102 MPa for CMC. ChNFs increase surface hydrophobicity and retard the scission of the C-H bond as a result of UV-light irradiation in both polymers under investigation. The yellowing from chain scission is reduced, while long-lasting retention of ductility is ensured. Given these results, we propose the utilization of ChNFs in sustainable polymeric materials from renewable carbon with competitive performance against fossil-based benchmark plastics.

Stimuli-responsive polymeric nanoparticles (NPs) can serve as smart drug delivery systems (DDSs) by triggering drug release upon external or internal stimuli. A dual-responsive DDS made of a triblock poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) (PCL-SS-PEG-SS-PCL) copolymer, bearing disulfide bonds between PCL and PEG, was synthesized. The copolymer was functionalized with coumarin and sensitive to near-infrared (NIR) light irradiation, while the S-S bonds could be cleaved by GSH (10 mM). Characterization was achieved by nuclear magnetic resonance, size exclusion chromatography, and Fourier transform infrared analyses. Nile Red (NR)-loaded NPs were prepared through self-assembly of the copolymer in water and analyzed by dynamic light scattering and field-emission scanning electron microscopy. The NR release upon ultraviolet (UV)/NIR light irradiation as well as by GSH concentrations was monitored by using fluorescence spectroscopy, while simultaneous exposure to UV/NIR light and intracellular GSH concentration led to faster NR release. AlamarBlue assay showed satisfactory cell viability of the NR-loaded NPs, while their cellular uptake in human dermal fibroblast cells was investigated by fluorescence microscopy and fluorescence emission measurements.

Elastin-like peptides (ELPs) exhibit lower critical solution temperature (LCST)-type behavior, being soluble at low temperatures and insoluble at high temperatures. While the properties of linear, long-chain ELPs are well-studied, short-chain ELPs, especially those with branched architectures, have been less explored. Herein, to obtain further insights into multimeric short ELPs, we investigated the temperature-responsive properties of branched molecules composed of a repeating pentapeptide unit of short ELPs, Phe-Pro-Gly-Val-Gly, as side components and oligo(Glu) as a backbone structure. In turbidimetry experiments, the branched ELPs showed LCST-like behavior similar to conventional ELPs and upper critical solution temperature (UCST)-like behavior, which are rarely observed in ELPs. In addition, the morphological aspects and mechanisms underlying the temperature-responsiveness were investigated. We observed that spherical aggregates formed, and the branched ELPs underwent structural changes through the self-assembly process. This study demonstrates the unique temperature-responsiveness of branched short ELPs, providing new insights into the future development and use of ELPs with tailored properties.

A drug delivery system based on silybin-conjugated chitosan (CS-SB) polymeric micelles was developed to improve the oral absorption of doxorubicin (DOX). SB was grafted to CS via succinic acid, and CS-SB was identified by ¹H NMR and FT-IR. The DOX-loaded micelles were prepared by self-assembly, and the characteristics of micelles, including a small particle size of 167.8 ± 2.3 nm, a high drug loading capacity of 8.59%, and a low critical micelle concentration of 1.3 × 10^-5 g/mL, were demonstrated. The micelles showed oral bioavailability of up to 193% versus DOX·HCl. The cytotoxicity test showed the biosafety of CS-SB and the potential of reductive DOX-induced cardiotoxicity. The inhibition of P-gp efflux and CYP3A4 enzyme in CS-SB micelles was confirmed by cellular uptake and enzyme activity inhibition tests. The endocytosis process of micelles was revealed by an endocytosis inhibition test. The findings exhibited the potential of CS-SB micelles in drug delivery.

The present work consist of the synthesis of photo-cross-linkable materials, based on unsaturated polyesters (UPs), synthesized from biobased monomers from renewable sources such as itaconic acid and 1,4-butanediol. The UPs were characterized to assess the influence of polycondensation reaction temperature and cross-linking time on their final properties. For this purpose, different UV irradiation exposure periods were tested. Homogeneous, uniform, and transparent films were obtained after 1, 3, and 5 min of UV exposure. These cross-linked films were then characterized. All materials presented high gel content, which was dependent on the reaction's temperature. The thermal behaviors of the UPs were shown to be similar. In vitro hydrolytic degradation tests showed that the materials can undergo degradation in phosphate-buffered saline (PBS) at pH 7.4 and 37 °C, ensuring their biodegradability over time. Finally, to assess the applicability of the polyesters as biomaterials, their cytocompatibility was determined by using human dermal fibroblasts.

Nanocarrier synthesis is highly process-dependent, leading to potential batch-to-batch variability if it is not controlled at each step. This variability affects the reproducibility of subsequent biomodification, resulting in unpredictable biological effects, particularly for bioactive molecules such as interleukin-2 (IL-2). Inconsistent conjugation can lead to variable treatment outcomes and severe side effects. Therefore, precise control of each synthesis step is critical for ensuring a consistent quality and biological performance. Our study demonstrates that dividing nanocarrier synthesis into smaller, controlled steps improves reproducibility. Using this method, we achieved highly reproducible, concentration-dependent growth of CTLL-2 cells with hydroxyethyl starch (HES) nanocapsules functionalized with defined amounts of IL-2. We believe that such detailed, stepwise control in nanocarrier synthesis enhances batch consistency, improving the clinical applicability of the drug delivery systems.

Hydrogels are indispensable for a variety of applications. Conventional biomaterial-based hydrogels, typically made from proteins or polysaccharides, often suffer from high costs, poor mechanical properties, and limited chemical functionality for modification. In this work, we present a novel hydrogel developed from modified castor oil, which is a renewable and cost-effective resource. Castor oil-based oligomer (CG) was synthesized using glycidyl methacrylate and triethylamine via ring-opening polymerization. The oligomer formed a gel only with Cu²⁺ ions among the various systematically studied metal ions. Comprehensive density functional theory calculations, atoms in molecules analysis, and steady and dynamic shear rheology were conducted to investigate the metal-binding sites and metal-oligomer interactions as well as the self-healing and viscoelastic properties of the oil-based hydrogels. The hydrogel exhibited 94% self-healing efficiency and performed as a recyclable rhodamine B dye adsorbent (73-90%). This innovative approach offers a novel, cost-effective, and sustainable alternative to traditional hydrogels, paving the way for advanced applications.

High-molecular-weight (HMW) (>500 kDa) glutaraldehyde-polymerized human hemoglobin (PolyhHb) is a promising hemoglobin-based oxygen carrier (HBOC) due to its decreased risk of vasoconstriction and oxidative tissue injury. Previously, HMW tense (T) quaternary state PolyhHb was synthesized at the pilot scale with tangential flow filtration (TFF) for the removal of low-molecular-weight species. However, T-state PolyhHb is limited to specific biomedical applications due to its low oxygen affinity, thus motivating the need to produce high oxygen affinity relaxed (R) quaternary state PolyhHb at the pilot scale. This study explored the pilot-scale synthesis and extensive biophysical characterization of both HMW T- and R-state PolyhHb. The resultant characterization demonstrated the successful synthesis of low and high oxygen affinity PolyhHb with increased molecular weight (∼1000-1500 kDa). Overall, T- and R-state PolyhHb provides a platform for manufacturing oxygen therapeutics with a diverse range of oxygen affinities and potential biomedical applications.