{"title":"Comparative Study of pH-Responsive and Aggregation Stability of Bosutinib-Loaded Nanogels Comprising Gelatin Methacryloyl, Carboxymethyl Dextran, and Hyaluronic Acid for Controlled Drug Delivery in Colorectal Cancer: An Extensive In Vitro Investigation.","authors":"Sankha Bhattacharya, Shashikant Bagade, Preeti Chidambar Sangave, Devendra Kumar, Imran Shaik, Dhrubojyoti Mukherjee","doi":"10.1021/acs.biomac.4c01209","DOIUrl":"10.1021/acs.biomac.4c01209","url":null,"abstract":"<p><p>This study investigates the use of pH-responsive nanogels for delivering Bosutinib (BOSU) in colon cancer treatment. Nanogels were formulated using three polymers: hyaluronic acid (HA), carboxymethyl dextran (CMD), and gelatin methacryloyl (GelMA). These nanogels achieved high drug entrapment efficiencies (80-90%) through polymer mixing with BOSU, followed by EDC/NHS cross-linking and sonication. The nanogels were stable, with negative zeta potentials (-20 to -30 mV) and particle sizes between 100 and 200 nm. Fourier-transform infrared analysis confirmed successful methacrylation in GelMA nanogels. Sustained BOSU release at pH 5.0 was observed, resembling tumor environments, compared to slower release at normal pH (7.4). Cytotoxicity tests showed 70-80% cell survival reduction in HCT116 colon cancer cells at higher doses, and GelMA-BOSU nanogels notably reduced cell migration. Antiangiogenic effects were confirmed in a chick chorioallantoic membrane model, highlighting the potential of these nanogels for targeted BOSU delivery in colon cancer therapy.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7926-7950"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-13DOI: 10.1021/acs.biomac.4c01355
Xuelin Zhang, Yexi Zhang, Xi Rong, Chuanmei Tang, Huiye Liu, Lei Yue, Rongxin Su, Yuefei Wang, Wei Qi
{"title":"Alkylated RALA-Derived Peptides for Efficient Gene Delivery.","authors":"Xuelin Zhang, Yexi Zhang, Xi Rong, Chuanmei Tang, Huiye Liu, Lei Yue, Rongxin Su, Yuefei Wang, Wei Qi","doi":"10.1021/acs.biomac.4c01355","DOIUrl":"10.1021/acs.biomac.4c01355","url":null,"abstract":"<p><p>RALA is an amphipathic cationic peptide demonstrated to be a low-toxicity and high-efficiency delivery platform for the systemic delivery of nucleic acid therapeutics. This work reports three RALA-derived peptides modified with N-terminal palmitic acid, engineered through amino acid substitutions and truncated sequences. All three peptides have good nucleic acid encapsulation, release and uptake, biocompatibility, and endolysosome escape. The siRNA transfection efficiency is about 90%, and the silencing rate of GA (C16-GLFWHHHARLARALARHLARALRA) exceeds that of lipofectamine 2000 (siRNA concentration = 50 nM). Truncating the peptide chain while retaining a certain amount of arginine ensures an effective particle size. Replacing glutamic acid with three histidines ensures an effective zeta potential and accelerates the endosome escape process through the proton sponge phenomenon. Introducing phenylalanine enhances the carrier-cell interaction. We believe that they are powerful carriers of siRNA therapy and may have good application prospects in treating various diseases.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"8046-8057"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-14DOI: 10.1021/acs.biomac.4c01286
Wei Gao, Huichun Kang, Ming Zhong, Lijuan Han, Xue Guo, Bitao Su, Ziqiang Lei
{"title":"Chitosan-Promoted TiO<sub>2</sub>-Loaded Double-Network Hydrogels for Dye Removal and Wearable Sensors.","authors":"Wei Gao, Huichun Kang, Ming Zhong, Lijuan Han, Xue Guo, Bitao Su, Ziqiang Lei","doi":"10.1021/acs.biomac.4c01286","DOIUrl":"10.1021/acs.biomac.4c01286","url":null,"abstract":"<p><p>The loading of photocatalysts on hydrogels can significantly reduce the loss of catalysts and effectively prevent secondary contamination, thus demonstrating great application potential and advantages in the field of wastewater treatment, especially in the removal of dyes. Herein, the semiconductor TiO<sub>2</sub> was successfully loaded into a polyacrylic acid/chitosan (PAA/CS) double-network (DN) hydrogel, which exhibited superior removal of dyes in wastewater such as MG, MB, MV, and RhB. The dye degradation process followed first-order kinetics, and the first-order rate constants for dye degradation were further calculated under UV light irradiation. Furthermore, the photocatalytic mechanism of the hydrogel was explored and analyzed. More interestingly, the PAA/CS-TiO<sub>2</sub> DN hydrogel has excellent tensile properties and superior electrical conductivity, which can be assembled into flexible sensors for real-time monitoring of mechanical deformations and human joint motions. It is envisioned that these excellent properties make hydrogel photocatalysts promising for a wide range of applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"8016-8025"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The Improved Redispersibility of Cellulose Nanocrystals Using Hydroxypropyl Cellulose and Structure Color from Redispersed Cellulose Nanocrystals.","authors":"Huan Wang, Lukuan Guo, Mingfeng Wu, Guang Chu, Wenyuan Zhu, Junlong Song, Jiaqi Guo","doi":"10.1021/acs.biomac.4c01277","DOIUrl":"10.1021/acs.biomac.4c01277","url":null,"abstract":"<p><p>Cellulose nanocrystals (CNC) have been significantly developed as a building block material for the design of novel functional materials in many fields such as biomedicine, nanotechnology, and materials science due to their excellent optical properties, biocompatibility, and sustainability. Improving the redispersibility of CNC in the sustainable processing of nanocellulose has been a challenge because intense hydrogen bond interaction leads to irreversible aggregation, making CNC difficult to redisperse and increasing the cost of storage and transportation of CNC. Hydroxypropyl cellulose (HPC) is an important hydroxy propylated cellulose ether. As a water-soluble cellulose derivative, HPC has a polyhydroxy structure similar to that of CNC, which leads to good compatibility and high affinity between HPC and CNC. In this work, HPC of different molecular weights was comixed with CNC of different contents, which was then dried using different methods, and the dried samples were redispersed in water. The addition of HPC improved the redispersibility of the CNC. Finally, the redispersed suspension was also redried to form a film, which was found to retain its structure color. These results provide an important avenue for the redispersion of dried CNC and for the development of functional materials from redispersed CNC.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"8006-8015"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-18DOI: 10.1021/acs.biomac.4c00915
Vyshakh M Panakkal, Dominik Havlicek, Ewa Pavlova, Klara Jirakova, Daniel Jirak, Ondrej Sedlacek
{"title":"Single-Step Synthesis of Highly Sensitive <sup>19</sup>F MRI Tracers by Gradient Copolymerization-Induced Self-Assembly.","authors":"Vyshakh M Panakkal, Dominik Havlicek, Ewa Pavlova, Klara Jirakova, Daniel Jirak, Ondrej Sedlacek","doi":"10.1021/acs.biomac.4c00915","DOIUrl":"10.1021/acs.biomac.4c00915","url":null,"abstract":"<p><p>Amphiphilic gradient copolymers are promising alternatives to block copolymers for self-assembled nanomaterials due to their straightforward synthesis via statistical copolymerization of monomers with different reactivities and hydrophilicity. By carefully selecting monomers, nanoparticles can be synthesized in a single step through gradient copolymerization-induced self-assembly (gPISA). We synthesized highly sensitive <sup>19</sup>F MRI nanotracers via aqueous dispersion gPISA of hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) with core-forming <i>N</i>,<i>N</i>-(2,2,2-trifluoroethyl)acrylamide (TFEAM). The PPEGMA-grad-PTFEAM nanoparticles were optimized to achieve spherical morphology and exceptional <sup>19</sup>F MRI performance. Noncytotoxicity was confirmed in Panc-1 cells. In vitro <sup>19</sup>F MR relaxometry and imaging demonstrated their diagnostic imaging potential. Notably, these gradient copolymer nanotracers outperformed block copolymer analogs in <sup>19</sup>F MRI performance due to their gradient architecture, enhancing <sup>19</sup>F relaxivity. The synthetic versatility and superior <sup>19</sup>F MRI performance of gradient copolymers highlight their potential in advanced diagnostic imaging applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7685-7694"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11632659/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-06DOI: 10.1021/acs.biomac.4c01245
Cole A Williams, Daniel J Stone, Soumil Y Joshi, Gokhan Yilmaz, Parisa Farzeen, Sungjin Jeon, Zamira Harris-Ryden, C Remzi Becer, Sanket A Deshmukh, Cassandra E Callmann
{"title":"Systematic Evaluation of Macromolecular Carbohydrate-Lectin Recognition Using Precision Glycopolymers.","authors":"Cole A Williams, Daniel J Stone, Soumil Y Joshi, Gokhan Yilmaz, Parisa Farzeen, Sungjin Jeon, Zamira Harris-Ryden, C Remzi Becer, Sanket A Deshmukh, Cassandra E Callmann","doi":"10.1021/acs.biomac.4c01245","DOIUrl":"10.1021/acs.biomac.4c01245","url":null,"abstract":"<p><p>The precise modulation of protein-carbohydrate interactions is critical in glycobiology, where multivalent binding governs key cellular processes. As such, synthetic glycopolymers are useful for probing these interactions. Herein, we developed precision glycopolymers (PGPs) with unambiguous local chemical composition and well-defined global structure and systematically evaluated the effect of polymer length, hydrophobicity, and backbone hybridization as well as glycan density and identity on the binding to both mammalian and plant lectins. Our studies identified glycan density as a critical factor, with PGPs below 50% grafting density showing significantly weaker lectin interactions. Coarse-grained molecular dynamics simulations suggest that the observed phenomena may be due to a decrease in carbohydrate-carbohydrate interactions in fully grafted PGPs, leading to improved solvent accessibility. In functional assays, these PGPs reduced the cell viability and migration in 4T1 breast cancer cells. Our findings establish a structure-activity relationship in glycopolymers, providing new strategies for designing synthetic glycomacromolecules for a myriad of applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7985-7994"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-22DOI: 10.1021/acs.biomac.4c01220
Huiru Wang, Shanyun Ma, Muyan Diao, Li Wenhui, Min Huan, Xiaofang Sun, Yuanzi Wu
{"title":"Engineering Thermoresponsive Enzyme-Polymer Conjugates via Glycan-Selective <i>In Situ</i> Polymerization for Recyclable Homogeneous Biocatalysis.","authors":"Huiru Wang, Shanyun Ma, Muyan Diao, Li Wenhui, Min Huan, Xiaofang Sun, Yuanzi Wu","doi":"10.1021/acs.biomac.4c01220","DOIUrl":"10.1021/acs.biomac.4c01220","url":null,"abstract":"<p><p>Enzymes are crucial for various technological applications, but their inherent instability and short lifespan pose challenges. This study presents facile immobilized enzyme technology with the development of thermoresponsive enzyme-polymer conjugates (EPCs), using glucose oxidase (GOx) as a model enzyme, to address these limitations. By conjugating heteropolymers to the glycan moieties of GOx through a precise <i>in situ</i> polymerization process, we could modulate the lower critical solution temperature of the EPCs, enhancing enzyme performance without compromising its active site. The EPCs demonstrate a switchable behavior that facilitates efficient homogeneous catalysis and easy heterogeneous separation, reducing costs and environmental impact in industrial applications. Our strategy presents a versatile platform for creating efficient biocatalysts with tunable properties, marking a step forward in sustainable and cost-effective bioprocessing.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7951-7957"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fungal Chitin Nanofibrils Improve Mechanical Performance and UV-Light Resistance in Carboxymethylcellulose and Polyvinylpyrrolidone Films.","authors":"Madalen Azpitarte Aretxabaleta, Gotzone Barandika, Rikardo Minguez, Erlantz Lizundia","doi":"10.1021/acs.biomac.4c00846","DOIUrl":"10.1021/acs.biomac.4c00846","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7630-7641"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Self-Healing, Electrically Conductive, Antibacterial, and Adhesive Eutectogel Containing Polymerizable Deep Eutectic Solvent for Human Motion Sensing and Wound Healing.","authors":"Shaghayegh Vakili, Zahra Mohamadnia, Ebrahim Ahmadi","doi":"10.1021/acs.biomac.4c00960","DOIUrl":"10.1021/acs.biomac.4c00960","url":null,"abstract":"<p><p>Flexible electronic devices such as wearable sensors are essential to advance human-machine interactions. Conductive eutectogels are promising for wearable sensors, despite their challenges in self-healing and adhesion properties. This study introduces a multifunctional eutectogel based on a novel polymerizable deep eutectic solvent (PDES) prepared by the incorporation of diallyldimethylammonium chloride (DADMAC) and glycerol in the presence of polycyclodextrin (PCD)/dopamine-grafted gelatin (Gel-DOP)/oxidized sodium alginate (OSA). The synthesized eutectogel has reversible Schiff-base bonds, hydrogen bonds, and host-guest interactions, which enable rapid self-healing upon network disruption. GPDO-15 eutectogel has significant tissue adhesion, high stretchability (419%), good ionic conductivity (0.79 mS·cm<sup>-1</sup>), and favorable antibacterial and self-healing properties. These eutectogels achieve 90% antibacterial effect, show excellent biocompatibility, and can be used as sensors to monitor human activities with strong stability and durability. The <i>in vivo</i> studies indicate that the eutectogels can improve the wound healing process which makes them an effective option for biological dressings.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7704-7722"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
BiomacromoleculesPub Date : 2024-12-09Epub Date: 2024-11-11DOI: 10.1021/acs.biomac.4c00889
Nancy Ferrentino, Taha Behroozi Kohlan, Shokoufeh Mehrtashfar, Anna Finne-Wistrand, Daniela Pappalardo
{"title":"Dual-Responsive Nanoparticles for Smart Drug Delivery: A NIR Light-Sensitive and Redox-Reactive PEG-PCL-Based System.","authors":"Nancy Ferrentino, Taha Behroozi Kohlan, Shokoufeh Mehrtashfar, Anna Finne-Wistrand, Daniela Pappalardo","doi":"10.1021/acs.biomac.4c00889","DOIUrl":"10.1021/acs.biomac.4c00889","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7660-7673"},"PeriodicalIF":5.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}