BiomacromoleculesPub Date : 2024-12-19DOI: 10.1021/acs.biomac.4c00959
Mohan Kavya, Varghese Priyanka, Alan Ranjit Jacob, P Nisha
{"title":"Investigating the Influence of Hydrogel and Oleogel Ratios on Physico Chemical Characteristics, Microstructure, Rheology, and Texture of a Food Grade Bigel.","authors":"Mohan Kavya, Varghese Priyanka, Alan Ranjit Jacob, P Nisha","doi":"10.1021/acs.biomac.4c00959","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c00959","url":null,"abstract":"<p><p>Bigels are promising technological advancements for application in the food industry, e.g., texture modification, controlled release, bioactive encapsulation, etc. Here, we focus on the fabrication and characterization of food-grade bigels from flaxseed-beeswax oleogel (OG) and pectin hydrogel (HG) under high shear conditions. Bigels were characterized by using FTIR, XRD, DSC, fluorescence microscopy, rheology, and texture analysis. Bigels retained the characteristics of both OG and HG, as evident from the OG's physical colloidal interactions and the HG's H-bonding in the bigel. Microscopic images revealed intricate network structures from both the HG and OG, with an increased OG fraction contributing to better homogeneity. The rheological properties of the bigels were in agreement with the textural attributes, revealing insights into the enhancement of tactile qualities. The synergistic effect of the OG and HG in bigels resulted in improved viscoelasticity and gel strength. Overall, the study helps in a holistic understanding of the interplay between composition and various attributes of bigels.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862521","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 : 2024-12-19DOI: 10.1021/acs.biomac.4c01279
Carolina Ordoñez, Marc A Dubé, Emily D Cranston, Marianna Kontopoulou, Timothy Morse, Gary A Deeter, Pascale Champagne, Michael F Cunningham
{"title":"Enhancing the Properties of Latex-Based Coatings with Carboxylated Cellulose Nanocrystals.","authors":"Carolina Ordoñez, Marc A Dubé, Emily D Cranston, Marianna Kontopoulou, Timothy Morse, Gary A Deeter, Pascale Champagne, Michael F Cunningham","doi":"10.1021/acs.biomac.4c01279","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01279","url":null,"abstract":"<p><p>Latex-based nanocomposites containing carboxylated cellulose nanocrystals (cCNCs) were synthesized via in situ seeded semibatch emulsion polymerization. Inspired by nature's use of CNCs to enhance rigidity and mechanical strength in cellulosic materials, we explored similar principles to improve the properties of acrylate water-based coatings. The cCNCs, loaded at 0.3-1.0 wt %, were added 1 h after pre-emulsion feeding began, addressing sensitivity to ionic strength and enabling stable final latexes. Careful control of the polymerization process maintained consistent particle sizes across formulations, allowing for mechanical property comparisons. Films from these latexes were evaluated through rheological and water sensitivity tests. With 1.0 wt % cCNC, significant increases in viscosity, shear-thinning behavior, stiffness, and elastic modulus were observed. Additionally, cCNCs reduced water and moisture absorption without affecting the whitening resistance. These findings demonstrate the enhanced properties of in situ cCNC latex nanocomposites, broadening their potential for industrial applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851660","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 : 2024-12-19DOI: 10.1021/acs.biomac.4c01500
Muireann Cosgrave, Kulwinder Kaur, Christopher Simpson, Łukasz Mielańczyk, Ciara Murphy, Robert D Murphy, Andreas Heise
{"title":"Tuning Star Polymer Architecture to Tailor Secondary Structures and Mechanical Properties of Diblock Polypeptide Hydrogels for Direct Ink Writing.","authors":"Muireann Cosgrave, Kulwinder Kaur, Christopher Simpson, Łukasz Mielańczyk, Ciara Murphy, Robert D Murphy, Andreas Heise","doi":"10.1021/acs.biomac.4c01500","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01500","url":null,"abstract":"<p><p>Hydrogel three-dimensional (3D) printing has emerged as a highly valuable fabrication tool for applications ranging from electronics and biomedicine. While conventional hydrogels such as gelatin, alginate, and hyaluronic acid satisfy biocompatibility requirements, they distinctly lack reproducibility in terms of mechanical properties and 3D printability. Aiming to offer a high-performance alternative, here we present a range of amphiphilic star-shaped diblock copolypeptides of l-glutamate and l-leucine residues with different topologies. Hydrophobic side chains of the l-leucine polymer block drive conformational self-assembly in water, spontaneously forming hydrogels with tunable mechanical properties, through variation of star topology. Their amenable shear-thinning and self-recovery properties render them suitable as hydrogel inks for direct ink writing. Well-defined 3D-printed structures can be readily generated and rapidly photo-cross-linked using visible light (405 nm) after methacrylamide functionalization, while hydrogel inks demonstrate good biocompatibility with top-seeded and encapsulated MC3T3 cells.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851601","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 : 2024-12-17DOI: 10.1021/acs.biomac.4c00648
Md Nasir Uddin, Md Abu Monsur Dinar, Leah E Schrass, Daniel W Pack, Jason E DeRouchey
{"title":"Impact of Acetylation, Succinylation, and pH on DNA Packaging in PEI-Based Polyplexes.","authors":"Md Nasir Uddin, Md Abu Monsur Dinar, Leah E Schrass, Daniel W Pack, Jason E DeRouchey","doi":"10.1021/acs.biomac.4c00648","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c00648","url":null,"abstract":"<p><p>Polyethylenimine (PEI) is a widely used cationic polymer for nonviral gene delivery, often modified to enhance transfection efficiency and reduce cytotoxicity. This study investigates how acetylation, succinylation (acPEI and zPEI), and pH influence the internal DNA packaging of polyplexes. Both modifications alter physicochemical properties, leading to complexes that decondense more readily with increasing modification. X-ray scattering reveals that high acetylation produces loosely packed DNA, while succinylation unexpectedly tightens DNA packing at higher modification levels. Polyplexes formed at low pH (pH 4) are more stable and tightly packed than those formed at pH 7.5. Acidifying polyplexes initially formed at pH 7.5 induces structural rearrangement to tighter DNA packing accompanied by significant PEI release, providing direct evidence for models where free PEI aids endosomal escape. These findings challenge conventional assumptions about PEI behavior and offer new insights into DNA packaging, emphasizing tailored polymer modifications and pH conditions to optimize gene delivery.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845301","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 : 2024-12-17DOI: 10.1021/acs.biomac.4c01020
Xianfeng Chu, Xiaowen Dou, Jiaying Yu, Junpeng Zhou, Di Ma, Miao Miao, Shaojun Hu, Kai Sun, Shihong Zhu, Qi Liu, Xiuming Zhang, Yong Jiang, Zhi-Fei Wang
{"title":"Synthesis of Polymers via Cancer Cell Metabolism-Mediated Controlled Radical Polymerization and Application in Engineering of Cell Surface.","authors":"Xianfeng Chu, Xiaowen Dou, Jiaying Yu, Junpeng Zhou, Di Ma, Miao Miao, Shaojun Hu, Kai Sun, Shihong Zhu, Qi Liu, Xiuming Zhang, Yong Jiang, Zhi-Fei Wang","doi":"10.1021/acs.biomac.4c01020","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01020","url":null,"abstract":"<p><p>In this study, we present a novel chemical biology strategy that leverages the reductive metabolic pathways of cancer cells to develop a new approach for synthesizing polymers in nonstrictly anaerobic conditions. This method utilizes the reductive metabolism of cancer cells to reduce Cu(II) to Cu(I), enabling Cu(I)-catalyzed controlled radical polymerization with poly(ethylene glycol) methyl ether methacrylate (MAPEGOMe) monomer, producing polymers with low dispersity (1.28-1.38). Furthermore, we found that this method could use MAPEGOMe as a monomer to in situ form a polymer layer on the initiator-modified cell surface, achieving a cell surface engineering modification. This study reveals the broad application value and potential of cancer cell metabolism-mediated controlled radical polymerization in the fields of chemical biology and polymer science.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845302","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 : 2024-12-17DOI: 10.1021/acs.biomac.4c01586
Elisa Impresari, Kaliroi Peqini, Tim P Hogervorst, Andrea Faustini, Francesca Bodega, Cristina Porta, Matteo Maria Pecchiari, Giuliano Zanchetta, Ilja K Voets, Stefano Pieraccini, Sara Pellegrino
{"title":"Gold Nanoparticles Decorated with HPLC6-Derived Peptides as a Platform for Ice Recrystallization Inhibition.","authors":"Elisa Impresari, Kaliroi Peqini, Tim P Hogervorst, Andrea Faustini, Francesca Bodega, Cristina Porta, Matteo Maria Pecchiari, Giuliano Zanchetta, Ilja K Voets, Stefano Pieraccini, Sara Pellegrino","doi":"10.1021/acs.biomac.4c01586","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01586","url":null,"abstract":"<p><p>In nature, organisms living in extreme environmental conditions produce antifreeze proteins (AFPs) that prevent the growth of ice crystals and depress the freezing point of body fluids. In this study, three different peptides derived from the N-terminal sequence of the helical type I AFP HPLC6, along with a stapled derivative produced via on-resin microwave-assisted copper(I)-catalyzed azide-alkyne cycloaddition, were conjugated to gold nanoparticles. The aim of decorating the surface of the nanoparticles with multiple copies of the peptides was to combine the ice-binding capability of the peptides with the size of a nanoparticle, thus, mimicking the protein bulkiness to enhance the peptide antifreeze activity. Ice recrystallization inhibition experiments on the functionalized gold nanoparticles showed a decrease in the ice crystal growth rates with the stapled conjugate being the most active. Conformational studies indicated a major helical content in the constrained peptide, highlighting the importance of a stable conformation for antifreeze activity. Finally, cytotoxicity tests showed that both the peptides and the nanoparticle constructs were nontoxic. The proposed approach could thus represent the starting point for developing effective strategies for cryopreservation.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833210","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 : 2024-12-17DOI: 10.1021/acs.biomac.4c01599
Dipankar Sahoo, Elena N Atochina-Vasserman, Juncheng Lu, Devendra S Maurya, Nathan Ona, Jessica A Vasserman, Houping Ni, Sydni Berkihiser, Wook-Jin Park, Drew Weissman, Virgil Percec
{"title":"Toward a Complete Elucidation of the Primary Structure-Activity in Pentaerythritol-Based One-Component Ionizable Amphiphilic Janus Dendrimers for In Vivo Delivery of Luc-mRNA.","authors":"Dipankar Sahoo, Elena N Atochina-Vasserman, Juncheng Lu, Devendra S Maurya, Nathan Ona, Jessica A Vasserman, Houping Ni, Sydni Berkihiser, Wook-Jin Park, Drew Weissman, Virgil Percec","doi":"10.1021/acs.biomac.4c01599","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01599","url":null,"abstract":"<p><p>Four-component lipid nanoparticles (LNPs) and viral vectors are key for mRNA vaccine and therapeutics delivery. LNPs contain ionizable lipids, phospholipids, cholesterol, and polyethylene glycol (PEG)-conjugated lipids and deliver mRNA for COVID-19 vaccines to liver when injected intravenously or intramuscularly. In 2021, we elaborated one-component ionizable amphiphilic Janus dendrimers (IAJDs) accessing targeted delivery of mRNA. Simplified synthesis and assembly processes allow for rapid IAJD screening for discovery. The role of the primary structure of IAJDs in activity indicated, with preliminary investigations, that ionizable amine (IA), sequence, and architecture of hydrophilic and hydrophobic domains are important for in vivo targeted delivery. Here, we study the role of the interconnecting linker length between the IA and the hydrophobic domain of pentaerythritol-based IAJDs. The linker length determines, through inductive effects, the position of the IA and the p<i>K</i><sub>a</sub> of the IAJDs and through flexibility, the stability of the DNPs, highlighting their extraordinarily important role in effective targeted delivery.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833212","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 : 2024-12-17DOI: 10.1021/acs.biomac.4c01246
Han Zhang, Shen Zhang, Minting Xie, Fachuang Lu, Fengxia Yue
{"title":"UV Resistance Properties of Lignin Influenced by Its Oxygen-Containing Groups Linked to Aromatic Rings.","authors":"Han Zhang, Shen Zhang, Minting Xie, Fachuang Lu, Fengxia Yue","doi":"10.1021/acs.biomac.4c01246","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01246","url":null,"abstract":"<p><p>The influence of lignin's primary oxygen-containing functional groups, phenolic OH (Ph-OH) and methoxyl (OMe) groups, especially the Ph-OH/OMe ratio, on its UV absorptivity and long-lasting UV blocking remains unclear. In this study, organosolv lignins (OLs) with varying Ph-OH and OMe contents were prepared to evaluate their UV absorptivity and photostability by EPR (electron paramagnetic resonance). As the Ph-OH contents increased from 0.32 to 6.09 mmol/g, lignin with a higher Ph-OH content displayed better absorptivity with a strong correlation (Pearson's <i>r</i> = 0.95). However, an excessive Ph-OH content (>5.5 mmol/g) reduced the spin content of lignin, negatively affecting its photostability. Taking Ph-OH and OMe groups as the cofactor, OLs with Ph-OH/OMe ratios between 0.44 and 0.64 showed more favorable UV-blocking performance both in the initial state and after UV irradiation. Moreover, lignin-based sunscreens exhibited increasing SPF value even after 8 h of UV exposure, confirming lignin's long-lasting UV-blocking property.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845303","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 : 2024-12-16DOI: 10.1021/acs.biomac.4c01672
Graham Michael Smeddle, Sébastien Lecommandoux
{"title":"<i>Biomacromolecules'</i> Year of Celebration.","authors":"Graham Michael Smeddle, Sébastien Lecommandoux","doi":"10.1021/acs.biomac.4c01672","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01672","url":null,"abstract":"","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833209","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 : 2024-12-16DOI: 10.1021/acs.biomac.4c01318
Stefano Elli, Tommaso Sisto, Sofia Nizzolo, Nadia Freato, Laura Bertocchi, Giulio Bianchini, Edwin A Yates, Marco Guerrini
{"title":"Modeling the Detailed Conformational Effects of the Lactosylation of Hyaluronic Acid.","authors":"Stefano Elli, Tommaso Sisto, Sofia Nizzolo, Nadia Freato, Laura Bertocchi, Giulio Bianchini, Edwin A Yates, Marco Guerrini","doi":"10.1021/acs.biomac.4c01318","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01318","url":null,"abstract":"<p><p>Hyaluronic acid (HA) is a natural and biocompatible polysaccharide that is able to interact with CD44 receptors to regulate inflammation, fibrosis, and tissue reconstruction. It is a suitable chemical scaffold for drug delivery that can be functionalized with pharmacophores and/or vectorizable groups. The derivatization of HA is achieved to varying extents by reacting 1-amino-1-deoxy-lactitol via the carboxyl group to form amide linkages, giving rise to the grafted polymer, HYLACH. This retains the broad properties of HA, even though, as in most HA-grafted polymers, the detailed conformational effects of such substitutions, while crucial in the design or optimization of drug delivery systems, remain unknown. Here, the conformation, size, secondary structure, hydrogen bond network, and hydration features of lactosylated HA derivatives were evaluated by using multiple independent molecular dynamics simulations. This revealed subtle but nevertheless significant changes in the HA scaffold, establishing the density of grafting as the key parameter determining its properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826520","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}