Biomacromolecules最新文献

{"title":"Molecular Dynamics Study of Hydrogen Bond Structure and Tensile Strength for Hydrated Amorphous Cellulose.","authors":"Tomoka Nakamura, Tatsuya Ishiyama","doi":"10.1021/acs.biomac.4c00950","DOIUrl":"10.1021/acs.biomac.4c00950","url":null,"abstract":"<p><p>Molecular dynamics (MD) simulations were conducted to investigate the hydrogen-bond (H-bond) structure and its impact on the tensile strength of hydrated amorphous cellulose. The study identifies a stable intramolecular H-bond between the hydroxyl group at position 3 and the ether oxygen at position 5 (OH3···O5). Intermolecularly, the hydroxyl groups at positions 2 (OH2) and 6 (OH6) form stable H-bonds. Young's modulus, maximum tensile strength, and corresponding strain were calculated as functions of moisture content, while the H-bond network, water cluster formation, and cellulose chain orientation during tensile simulations were analyzed to elucidate mechanical properties. The substitution effect of cellulose on Young's modulus is also examined, revealing that the substitution of OH3 for a hydrophobic group minimally affects Young's modulus, but substitutions at OH2 and OH6 significantly reduce tensile strength due to their roles as key intermolecular H-bond donor sites.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7249-7259"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453418","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":"Switchable pH-Responsive Morphologies of Coassembled Nucleobase Copolymers.","authors":"Laura Vasilica Arsenie, Mona Semsarilar, Belkacem Tarek Benkhaled, Amine Geneste, Benedicte Prélot, Olivier Colombani, Erwan Nicol, Patrick Lacroix-Desmazes, Vincent Ladmiral, Sylvain Catrouillet","doi":"10.1021/acs.biomac.4c00901","DOIUrl":"10.1021/acs.biomac.4c00901","url":null,"abstract":"<p><p>This work presents supramolecular coassembled nucleobase copolymers with transitional morphologies upon pH changes (from 7.4 to 10). Uracil- and adenine-containing copolymers were prepared by RAFT, which allowed us to finely tailor the polymerization degree and the composition. The coassembled formulations prepared in an aqueous buffer at two distinct pH (7.4 and 10) formed spherical morphologies at physiological pH. The increase of the pH induced the apparition of various large, irreversible anisotropic supramolecular architectures. Isothermal titration calorimetry revealed that the coassembly at pH 7.4 was mainly guided by H-bonds between complementary nucleobases, while the experiments conducted at pH 10 showed that the assemblies were mainly driven by hydrophobic interactions. These results highlight that the nature of supramolecular interactions (H-bonds or hydrophobic interactions) has a great influence on the morphology of nucleobase-containing coassemblies when changing the pH. These findings may provide further perspectives in the field of advanced nanomaterials.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7225-7236"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491098","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":"Intestinal-Target and Glucose-Responsive Smart Hydrogel toward Oral Delivery System of Drug with Improved Insulin Utilization.","authors":"Rui Ying, Wei Wang, Rui Chen, Ruoyu Zhou, Xiangzhao Mao","doi":"10.1021/acs.biomac.4c01093","DOIUrl":"10.1021/acs.biomac.4c01093","url":null,"abstract":"<p><p>An intelligent insulin delivery system targeting intestinal absorption and glucose responsiveness can enhance the bioavailability through oral insulin therapy, offering promising diabetes treatment. In this paper, a glucose and pH dual-response polymer hydrogel using carboxymethyl agarose modified with 3-amino-phenylboronic acid and l-valine (CPL) was developed as an insulin delivery carrier, exhibiting excellent biocompatibility and effective insulin encapsulation. The insulin encapsulated in the hydrogel (Ins-CPL) was released in a controlled manner in response to the <i>in vivo</i> stimulation of blood glucose and pH levels with higher levels of intracellular uptake and utilization of insulin in the intestinal environment simultaneously. Notably, the Ins-CPL hydrogel effectively regulated blood sugar in diabetic rats over a long period by simulating endogenous insulin, responding to changes in plasma pH and glucose levels, and overcoming the intestinal epithelium barrier. This indicates a significant boost in oral insulin bioavailability and broadens its application prospects.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7446-7458"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453416","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":"Melt Polycondensation Strategy to Access Unexplored l-Amino Acid and Sugar Copolymers.","authors":"Dheeraj Chandra Joshi, Utreshwar Arjun Gavhane, Manickam Jayakannan","doi":"10.1021/acs.biomac.4c00993","DOIUrl":"10.1021/acs.biomac.4c00993","url":null,"abstract":"<p><p>Biodegradable polymers from bioresources are highly in demand for the development of sustainable polymer platforms for commodity plastics and in the biomedical field. Here, an elegant one-pot synthetic strategy is developed, for the first time, to access unexplored hybrid polymers from two naturally abundant resources: carbohydrates (sugars) and l-amino acids. A bottleneck in the synthetic strategy is overcome by tailor-making d-mannitol-based six- and five-membered bicyclic acetalized diols, and their structures are confirmed by single-crystal X-ray diffraction and 2D NMR spectroscopy. l-Amino acids are converted into ester-urethane functional monomers, and they are polymerized with sugar-diols under solvent-free melt polycondensation to yield biodegradable poly(ester-urethane)s. Acid-catalyzed deprotection yielded amphiphilic polymers having exclusively alternating residues of sugar and l-amino acid in the polymer backbone. The polymer is self-assembled into 200 ± 10 nm sized nanoparticles that can encapsulate fluorescent dyes, are nontoxic to cells up to 250 μg/mL, and are readily endocytosed for lysosomal enzymatic biodegradation at the cellular level.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7311-7322"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453417","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":"Orientation Distribution of Crystalline β-Sheet Domains in <i>Bombyx mori</i> Silk Fiber Studied with Vibrational Sum Frequency Generation Spectroscopy.","authors":"Jihyeong Ryu, Juseok Choi, Jongcheol Lee, Seong H Kim","doi":"10.1021/acs.biomac.4c00774","DOIUrl":"10.1021/acs.biomac.4c00774","url":null,"abstract":"<p><p>Silk fibers have good biocompatibility and mechanical properties, which make them attractive in biomaterial applications as well as textile industries. It is believed that the superior mechanical property is associated with the crystalline β-sheet structure in the fiber; but a deeper understanding of the structure-property relationship is still needed for full exploitation of its physical properties. Especially, accurate information on hydrogen-bonding interactions within β-sheet domains at the nanoscale and their spatial distributions at the mesoscale are critically needed. In this study, we demonstrate the selective detection of crystalline β-sheet domains in <i>Bombyx mori</i> silk fiber using sum frequency generation (SFG) spectroscopy and its use to determine the angular distribution of the β-sheet crystallites with respect to the fiber axis. Numerical simulations of the SFG signal of the amide-I band were carried out using tensors based on the B2 symmetry of the D₂ point group and compared with experimental data. This comparison found that the crystalline β-sheet domains are aligned along the fiber axis with a standard deviation of ∼27° and parallel to the fiber surface with a standard deviation of ∼5°. It was also found that the amide bands in the SFG spectra cannot be fully explained with the assumption that the crystalline β-sheet vibrations can be described with the D₂ point group. Being able to monitor the amide group vibrations sensitive to both interchain hydrogen bonding and crystallite orientations, SFG analysis has a potential to unveil the structure-mechanical property relationship that may not be readily assessable with other characterization techniques.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7178-7190"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453420","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":"Understanding Polyproline's Unusual Thermoresponsive Properties Using a Polyproline-Based Double Hydrophilic Block Copolymer.","authors":"Arjun Singh Bisht, Ankita Kumari, Ankita Meena, Raj Kumar Roy","doi":"10.1021/acs.biomac.4c00768","DOIUrl":"10.1021/acs.biomac.4c00768","url":null,"abstract":"<p><p>Polyproline is a unique thermoresponsive polymer characterized by large thermal and conformational hysteresis. This article employs polyproline-based double hydrophilic block copolymers (PNIPAM_<i>n</i>-<i>b</i>-PLP_<i>m</i>) to gain insight into polyproline's thermoresponsive mechanism. The amine-terminated poly(<i>N</i>-isopropylacrylamide) (NH₂-PNIPAM_<i>m</i>) was used as the macroinitiator for ring-opening polymerization of proline-NCA monomers, resulting in various block copolymers (PNIPAM_<i>n</i>-<i>b</i>-PLP_<i>m</i>) with varying PLP block lengths. Block copolymers' thermal phase transitions were compared with their homopolymer counterparts using turbidimetry, variable-temperature NMR, dynamic light scattering, and circular dichroism spectroscopy. These experiments revealed that regardless of their compositions, all block copolymers exhibited a two-stage collapse (<i>T</i>_CP(PLP) > <i>T</i>_CP(PNIPAM)) during the heating cycle. In contrast, only one clearing temperature (<i>T</i>_CL) was observed during cooling. The observed clearing temperature is closely correlated to the clearing temperature of PNIPAM blocks, suggesting the role of water-soluble PNIPAM blocks in resolving the PLP blocks. Moreover, thermal and conformational hysteresis related to the polyproline block is significantly suppressed in the presence of a PNIPAM block. Linking PNIPAM blocks has two significant effects on PLP segments' thermoresponsive behavior. For example, during the heating cycle, the precollapsed PNIPAM chains (as <i>T</i>_CP(PNIPAM) < <i>T</i>_CP(PLP)) prevent orderly aggregation within the PLP block. Meanwhile, during the cooling cycle below the clearing temperature of the PNIPAM block, the PNIPAM chains impart water solubility (as <i>T</i>_CL(PNIPAM) > <i>T</i>_CL(PLP)) to the collapsed PLP chains. Overall, the PNIPAM block imparts water solubility and perturbs PLP chains to form the native aggregate structure, suppressing the hysteresis effect. Accordingly, the large thermal and conformational hysteresis associated with native PLP chains appears to result from a noninterfering aggregation above the critical temperature.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7167-7177"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453426","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":"Ultrasensitive <i>In Vitro</i> and <i>Ex Vivo</i> Tracking of ¹³C-Labeled PEG-PLA Degradation Products by MALDI-TOF Mass Spectrometry.","authors":"Minh-Thuong Khong, Vincent Darcos, Jérôme Vialaret, Feifei Ng, Guillaume Couture, Marie-Emérentienne Cagnon, Adolfo L Noriega, Jana Kindermans, Xavier Garric, Christophe Hirtz, Benjamin Nottelet","doi":"10.1021/acs.biomac.4c01169","DOIUrl":"10.1021/acs.biomac.4c01169","url":null,"abstract":"<p><p>Copolymers of poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) are widely used in biomedical applications. As inactive ingredients in formulations, tracking their degradation byproducts <i>in vivo</i> stands as a major challenge but is a pivotal endeavor to ensure safety and further progress in clinical stages. Current bioanalytical methods used to monitor this degradation lack sensitivity and quantification precision. This study introduces a cost-effective synthetic route for ¹³C-labeled PEG-PLA copolymers, combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), to monitor their <i>in vitro</i> and <i>ex vivo</i> degradation. Incorporating ¹³C isotopes into copolymers significantly enhances MALDI-TOF sensitivity, allowing for precise detection of degradation products at exceedingly low concentrations. We demonstrate the ability to trace ¹³C-labeled PEG-PLA in complex biological media (urine, plasma) at concentrations 100 times lower than labeled PEG-PLA. Our results pave the way toward ultrasensitive <i>in vivo</i> tracking and elucidation of <i>in vivo</i> fate of this widely investigated polymer family.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"7485-7499"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491100","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":"External Bleeding and Advanced Biomacromolecules for Hemostasis.","authors":"Sajjad Fanaee, William Austin, Mark Filiaggi, Vahid Adibnia","doi":"10.1021/acs.biomac.4c00952","DOIUrl":"10.1021/acs.biomac.4c00952","url":null,"abstract":"<p><p>Hemorrhage is a significant medical problem that has been an active area of research over the past few decades. The human body has a complex response to bleeding that leads to blood clot formation and hemostasis. Many biomaterials based on various biomacromolecules have been developed to either accelerate or improve the body's natural response to bleeding. This review examines the mechanisms of hemostasis, types of bleeding, and the <i>in vitro</i> or <i>in vivo</i> models and techniques used to study bleeding and hemostatic materials. It provides a detailed overview of the diverse hemostatic materials, including those that are highly absorbent, wet adhesives, and those that accelerate the biochemical cascade of blood clotting. These materials are currently marketed, under preclinical testing, or being researched. In exploring the latest advancements in hemostatic technologies, this paper highlights the potential of these materials to significantly improve bleeding control in clinical and emergency situations.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"6936-6966"},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491090","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":"Progress in Multiscale Modeling of Silk Materials.","authors":"Harry D A Brough, David Cheneler, John G Hardy","doi":"10.1021/acs.biomac.4c01122","DOIUrl":"10.1021/acs.biomac.4c01122","url":null,"abstract":"<p><p>As a result of their hierarchical structure and biological processing, silk fibers rank among nature's most remarkable materials. The biocompatibility of silk-based materials and the exceptional mechanical properties of certain fibers has inspired the use of silk in numerous technical and medical applications. In recent years, computational modeling has clarified the relationship between the molecular architecture and emergent properties of silk fibers and has demonstrated predictive power in studies on novel biomaterials. Here, we review advances in modeling the structure and properties of natural and synthetic silk-based materials, from early structural studies of silkworm cocoon fibers to cutting-edge atomistic simulations of spider silk nanofibrils and the recent use of machine learning models. We explore applications of modeling across length scales: from quantum mechanical studies on model peptides, to atomistic and coarse-grained molecular dynamics simulations of silk proteins, to finite element analysis of spider webs. As computational power and algorithmic efficiency continue to advance, we expect multiscale modeling to become an indispensable tool for understanding nature's most impressive fibers and developing bioinspired functional materials.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"6987-7014"},"PeriodicalIF":8.3,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11558682/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491095","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}

{"title":"Fibrillar Hydrogel Inducing Cell Mechanotransduction for Tissue Engineering.","authors":"Viktoriia V Egorova, Mariia P Lavrenteva, Liubov N Makhaeva, Ekaterina A Petrova, Alina A Ushakova, Mikhail S Bozhokin, Elena F Krivoshapkina","doi":"10.1021/acs.biomac.4c00897","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c00897","url":null,"abstract":"<p><p>One of the key strategies for tissue engineering is to design multifunctional bioinks that balance printability with cytocompatibility. Here, we describe fibrillar hydrogels produced by Schiff base formation between B-type gelatin and oxidized sodium alginate, followed by the incorporation of type I collagen, yielding a new gel (MyoColl). The resulting hydrogel exhibits a temperature- and mass-ratio-dependent sol-gel transition, showing variability of hydrogel properties depending on the component ratio. MyoColl composition provides a convenient platform for biofabrication in terms of shear thinning, yielding, Young's modulus, and shape accuracy. Metabolic activity tests and fluorescent microscopy of 2D hydrogel-based mouse C2C12 myoblast cell culture show significant cytocompatibility of the developed carriers. In addition, primary signs of cell mechanotransduction and myofilament formation of 3D printed MyoColl-based cell cultures were detected and described. Due to these promising results, the described hydrogel composition has shown itself as a convenient platform for muscle tissue engineering.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612616","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}