{"title":"The Influence of DNA Handles on the Mechanical Response of Single Protein Molecules.","authors":"Sabita Sharma, Sadia Rahman, Mattan Ze'ev Becker, Maya Georgia Pelah, Ronen Berkovich, Ionel Popa","doi":"10.1021/acs.biomac.5c00429","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00429","url":null,"abstract":"<p><p>The mechanical response of proteins to force is governed by their chain stiffness, molecular length, and domain segmentation and can be influenced by unstructured tethers in series with the molecule. Here, we investigate the effect of DNA linkers on the mechanical unfolding of proteins. These tethers are extensively used in single-molecule techniques as spacing handles or calibration standards. We designed two DNA-protein constructs made from covalently cross-linked DNA molecules having 604 bp and 3 kbp in series with eight repeats of bacterial protein L, and compared them with the protein L construct lacking any DNA linker. Using magnetic tweezers, we measured the unfolding dynamics and folding likelihood of protein L connected in series with these DNA linkers. Our findings indicate that stiff DNA linkers do not significantly alter the unfolding kinetics of the tethered protein, while a longer handle slightly increases the force required for refolding. We rationalize our measurements using an energy profile model projected on the pulling end-to-end reaction coordinate. Furthermore, we analyze how the tension is being transmitted along the protein-DNA construct as a function of its size. We conclude that the small differences induced by the presence of DNA linkers in single-molecule measurements are insignificant, given the current instrumental capabilities.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951546","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 : 2025-05-13DOI: 10.1021/acs.biomac.5c00386
Yuna Lee, Juneha Bak
{"title":"Rheological Properties of Fucoidan-Xanthan Gum Mixture in the Presence of Simulated Salivary Fluid and Its Anti-Inflammatory Effect after <i>In Vitro</i> Digestion.","authors":"Yuna Lee, Juneha Bak","doi":"10.1021/acs.biomac.5c00386","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00386","url":null,"abstract":"<p><p>Fucoidan, known for its anti-inflammatory effects, holds potential in functional beverages, especially for elderly individuals. For those with dysphagia, thickeners such as xanthan gum (XG) should be used at high concentrations (≥1.0%) to achieve the desired viscosity. This study explores the influence of saliva on the rheological characteristics of fucoidan-XG mixtures using artificial simulated saliva fluid (SSF), as well as the effect of 1.0% XG on fucoidan's anti-inflammatory effects after digestion using the INFOGEST digestion model. All mixtures exhibited a shear-thinning flow behavior. Due to the dilution effect of SSF, the apparent viscosity and viscoelastic moduli of the mixtures decreased. However, improved rheological properties were observed in SSF-mixed mixtures compared to those mixed with water due to salt-induced cross-linking. Both digested fucoidan and fucoidan-XG mixtures reduced IL-6 and TNF-α production in lipopolysaccharide-stimulated RAW264.7 macrophages, with lower IL-6 levels in the mixtures compared to fucoidan alone at low fucoidan concentrations (≤1.0%).</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953302","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 : 2025-05-12Epub 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":"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":"2800-2810"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","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 : 2025-05-12Epub Date: 2025-04-14DOI: 10.1021/acs.biomac.4c01505
Ali Maruf, Małgorzata Milewska, Katarzyna Dudzisz, Anna Lalik, Sebastian Student, Anna Salvati, Ilona Wandzik
{"title":"Trehalose-Releasing Nanogels: Study on Trehalose Release and Insights into Selected Biologically Relevant Aspects.","authors":"Ali Maruf, Małgorzata Milewska, Katarzyna Dudzisz, Anna Lalik, Sebastian Student, Anna Salvati, Ilona Wandzik","doi":"10.1021/acs.biomac.4c01505","DOIUrl":"10.1021/acs.biomac.4c01505","url":null,"abstract":"<p><p>Trehalose has sparked considerable interest in a variety of pharmaceutical applications as well as in cryopreservation. Recently, there have been growing efforts in the development of trehalose delivery nanocarriers to address the issue of the poor bioavailability of trehalose. The majority of the strategies comprise physical entrapment of trehalose, since its covalent, yet biolabile, conjugation is challenging. Here, we present research on trehalose-releasing nanogels, in which covalent, yet biolabile, conjugation of trehalose was achieved through the co-incorporation of trehalose (meth)acrylate(s) together with hydrophilic primary/secondary acrylamides in one polymeric network. In this case, the primary and secondary amide groups participated in ester hydrolysis in the (meth)acrylate units, making the hydrolysis feasible under physiologically relevant conditions. A set of nanogels with precisely selected compositions were synthesized, characterized, and then studied to evaluate the influence of various structural and environmental factors on the release rate of trehalose. The study also provides insights into some other aspects that are important in view of potential biomedical applications, including specific interactions of nanogels through their terminal α-d-glucopyranosyl moieties from pendant trehalose, protein corona formation, and cellular uptake.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2835-2851"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076505/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952150","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":"Water and Collagen: A Mystery Yet to Unfold.","authors":"Guido Giannetti, Fumiki Matsumura, Federico Caporaletti, Dimitra Micha, Gijsje H Koenderink, Ioana Mariuca Ilie, Mischa Bonn, Sander Woutersen, Giulia Giubertoni","doi":"10.1021/acs.biomac.4c01735","DOIUrl":"10.1021/acs.biomac.4c01735","url":null,"abstract":"<p><p>Collagen is the most abundant protein in the human body and plays an essential role in determining the mechanical properties of the tissues. Both as a monomeric protein and in fibrous assemblies, collagen interacts with its surrounding molecules, in particular with water. Interestingly, while it is well established that the interaction with water strongly influences the molecular and mechanical properties of collagen and its assemblies, the underlying mechanisms remain largely unknown. Here, we review the research conducted over the past 30 years on the interplay between water and collagen and its relevance for tissue properties. We discuss the water-collagen interaction on relevant time- and length scales, ranging from the vital role of water in stabilizing the characteristic triple helix structure to the negative impact of dehydration on the mechanical properties of tissues. A better understanding of the water-collagen interaction will help to unravel the effect of mutations and defective collagen production in collagen-related diseases and to pinpoint the key design features required to synthesize collagen-based biomimetic tissues with tailored mechanical properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2784-2799"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076498/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955260","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 : 2025-05-12Epub Date: 2025-04-12DOI: 10.1021/acs.biomac.5c00018
Jiaquan Hong, Bocheng Xu, Xiaole Hu, Chun Liu, Hongsheng Liu, Jinhuan Tian, Lihua Li, Shan Ding, Changren Zhou, Lu Lu
{"title":"Hyaluronic Acid Microneedles Loaded with Chinese Herbal Extracts as an Intradermal Delivery System for Hair Regeneration.","authors":"Jiaquan Hong, Bocheng Xu, Xiaole Hu, Chun Liu, Hongsheng Liu, Jinhuan Tian, Lihua Li, Shan Ding, Changren Zhou, Lu Lu","doi":"10.1021/acs.biomac.5c00018","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00018","url":null,"abstract":"<p><p>Androgenic alopecia is one of the most common chronic problems for dermatologists worldwide. Some Chinese herbal extracts have been shown to promote hair growth, but the active ingredients are difficult to enter the dermis. Therefore, delivering the active ingredients into the dermis becomes a key factor. Herein, <i>Platycladus orientalis</i> leaf extract (PO-ex) was obtained using ethanol as a solvent, and then hyaluronic acid methacrylate/hyaluronic acid (HAMA/HA) hydrogel was loaded with PO-ex to prepare hyaluronic acid microneedles (PO-ex MN). The double cross-linked HAMA/HA provides sufficient mechanical strength to pierce the stratum corneum and deliver PO-ex into the dermis; PO-ex can effectively improve the environment for hair follicle cell proliferation by removing reactive oxygen free radicals; in addition, the self-repair reaction caused by microneedle mechanical stimulation activates the Wnt/β-catenin pathway associated with trauma repair and promotes hair follicle growth. PO-ex MN is a potential therapeutic strategy for the treatment of androgenic alopecia.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2945-2959"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951240","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":"Mechanically Activated Starch Reticular Nanostructure Traps Ferulic Acid as a Structural and Functional Cargo.","authors":"Siyu Yao, Haohao Hu, Yushi Li, Qingqing Zhu, Huan Cheng, Mingming Guo, Donghong Liu, Enbo Xu","doi":"10.1021/acs.biomac.5c00335","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00335","url":null,"abstract":"<p><p>Upon the scalable utilization of polyphenols, the design of their composites with polymers has received a great deal of attention. However, the starch polymer has a weak loading of hydrophobic polyphenols typically through noncovalent interactions without biochemical catalysts. Here, we tailor a reticular starch nanostructure from a starch nanosphere precursor (preSNS) that traps ferulic acid (FA) via esterification. The preSNS-FA network is activated by a green physical method via dynamic high-pressure microfluidization, exhibiting an exceptionally higher content of FA (∼38.0%) compared with the conventional starch group (only ∼1.5%). SEM, FTIR, XRD, 13C NMR, 1H NMR, and XPS results as well as molecular dynamics simulation comprehensively confirm the changes in architecture and hydrogen bonding modes with the formation of -COOR-. The preSNS-FA network also has an enzymatic hydrolysis resistance (up to 83.8%). Collectively, this work establishes a high-performance and catalyst-free synthetic route toward an esterified polyphenol complex network with potential applications in nutrient delivery, food packaging, and agriculture fields.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952070","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 : 2025-05-12Epub Date: 2025-04-10DOI: 10.1021/acs.biomac.5c00133
Yuki Hirayama, Atsushi Maruyama, Naohiko Shimada
{"title":"Photo-Switching from Enzymatic Reaction to DNA Self-Assembly Enabled by a Caged Cationic Copolymer.","authors":"Yuki Hirayama, Atsushi Maruyama, Naohiko Shimada","doi":"10.1021/acs.biomac.5c00133","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00133","url":null,"abstract":"<p><p>Enzymatic reactions that act on DNA and DNA self-assembly reactions have been harnessed to create sophisticated dynamic DNA nanodevices. Methods for temporally and spatially controlling these reactions will enable creation of more advanced DNA nanodevices. We previously reported that cationic graft copolymers activate DNA self-assembly reactions including DNA hybridization and strand displacement reactions while inhibiting reactions catalyzed by enzymes that act on DNA. In this study, we prepared a photoactivatable graft copolymer as a tool to spatiotemporally switch between enzymatic and self-assembly reactions upon photoirradiation. The graft copolymer caged at their amino groups with photocleavable 6-nitroveratryloxycarbonyl moieties did not inhibit polymerase reactions and did not activate toehold-mediated strand displacement reactions. After UV irradiation to uncage the amino groups of the copolymer, polymerase activity was inhibited and toehold-mediated strand displacement was activated. Thus, remote switching from polymerization to toehold-mediated strand displacement was performed by photoirradiation.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"3059-3064"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952456","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 : 2025-05-12Epub Date: 2025-04-21DOI: 10.1021/acs.biomac.5c00263
William R Lowery, Allison C Portaro, G Kane Jennings, David E Cliffel
{"title":"Photosystem I Photopolymerizes Pyrrole into Spherical Nanocomposites.","authors":"William R Lowery, Allison C Portaro, G Kane Jennings, David E Cliffel","doi":"10.1021/acs.biomac.5c00263","DOIUrl":"10.1021/acs.biomac.5c00263","url":null,"abstract":"<p><p>Conductive polymers have been shown to be an effective scaffold for proteins when designing bioelectrochemical systems, particularly for the Photosystem I protein. Utilization of synthetic polymer chemistry has allowed a great deal of tunability within the protein/polymer interface to improve electron transfer from the proteins, ultimately progressing toward direct electron transfer from the active sites. Seeking to address this issue, a new heterogeneous approach is presented to synthesize Photosystem I/polypyrrole (PSI/PPy) composites. The oxidative potential of PSI's P<sub>700</sub> reaction site was leveraged to polymerize pyrrole into a molecular wire, providing a more efficient means of electron transfer to the protein. Over the course of several hours of photopolymerization of Py in a PSI film, PPy not only wired PSI but began incasing the protein within conductive polymer nanoparticles. These resulting composite nanoparticles were extensively characterized by electron microscopy and electrochemical techniques to showcase their synergistic properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"3180-3185"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076494/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951096","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":"Antibacterial and Cell-Adhesive Poly(2-ethyl-2-oxazoline) Hydrogels Developed for Wound Treatment: <i>In Vitro</i> Evaluation.","authors":"Senem Buyuksungur, Tugba Endogan Tanir, Vasif Hasirci, Nesrin Hasirci","doi":"10.1021/acs.biomac.5c00181","DOIUrl":"10.1021/acs.biomac.5c00181","url":null,"abstract":"<p><p>Poly(2-alkyl-2-oxazoline) (PAOx) polymers are promising materials due to their tunable properties. In this study, poly(2-ethyl-2-oxazoline) (PEtOx) was methacrylated after partial hydrolysis to produce methacrylated poly(2-ethyl-2-oxazoline) (POx-MA), which was subsequently used to synthesize novel hydrogels. Interpenetrating polymer networks (IPN) were developed by combining POx-MA with methacrylated gelatin (GelMA). Compression tests revealed that GelMA exhibited the highest mechanical strength (199 ± 21 kPa), followed by the IPN POx-MA:GelMA (112 ± 27 kPa) and POx-MA (15 ± 5 kPa). However, in scratch wound healing tests, this order was reversed, with POx-MA exhibiting the highest closure (67 ± 8%), followed by the IPN (51 ± 2%) and GelMA (42 ± 1%) in 48 h. Cell viability exceeded 90% with all of the hydrogels. The study showed that partial hydrolysis and the resultant free amine groups in POx-MA enhanced cell adhesion. Moreover, POx-MA containing hydrogels demonstrated high antibacterial activity against <i>Escherichia coli</i> and <i>Staphylococcus aureus</i>. This study highlights the superior properties of POx-MA and POx-MA:GelMA IPN as novel hydrogels with substantial potential for biomaterials and tissue engineering applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"3139-3154"},"PeriodicalIF":5.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12076500/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143954887","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}