Biomacromolecules最新文献

Engineered Assemblies from Constitutionally Isomeric Peptides Modulate Antimicrobial Activity.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-28 DOI: 10.1021/acs.biomac.5c00071

Yujia Lu, Guanyi Li, Yanwen Zhang, Yuxuan Ge, Bin Hao, Yu Yin, Yaxue Zhao, Yin Wang

{"title":"Engineered Assemblies from Constitutionally Isomeric Peptides Modulate Antimicrobial Activity.","authors":"Yujia Lu, Guanyi Li, Yanwen Zhang, Yuxuan Ge, Bin Hao, Yu Yin, Yaxue Zhao, Yin Wang","doi":"10.1021/acs.biomac.5c00071","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00071","url":null,"abstract":"Antimicrobial peptides (AMPs) are a class of peptides consisting of cationic amino acid residues and a hydrophobic segment, which have been used as an alternative to antibiotics in treating multidrug-resistant bacteria. However, the relationship among the molecular design, assembled structures, and resultant efficacy remains elusive. Herein, we report a class of constitutionally isomeric AMPs assembled into filaments with similar dimensions. Spectroscopic characterizations demonstrated that subtle changes in the position of amino acids led to dramatic variations in molecular packing and surface charges, which were verified by molecular dynamics simulations. In vitro antibacterial assays showed that all AMPs exerted antibacterial activity against Gram-positive methicillin-resistant Staphylococcus aureus (MRSA), but the efficacy was dependent on the molecular design. Given the good biocompatibility to eukaryotic cells, these AMPs could be potentially used as antibacterial agents. We believe that this finding provides an avenue to tune the bioactivity of AMPs by rational molecular design.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727018","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}

引用次数: 0

Dual-Responsive Ultrathin Peptoid Nanofibers Assembled from Amphiphilic Alternating Peptoids with an Integration of Azobenzene and Histamine Moieties.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-27 DOI: 10.1021/acs.biomac.5c00211

Mingyu Ding, Qianyu Jiang, Pengchao Wu, Pengliang Sui, Zichao Sun, Xiaoling Yang, Haibao Jin, Shaoliang Lin

{"title":"Dual-Responsive Ultrathin Peptoid Nanofibers Assembled from Amphiphilic Alternating Peptoids with an Integration of Azobenzene and Histamine Moieties.","authors":"Mingyu Ding, Qianyu Jiang, Pengchao Wu, Pengliang Sui, Zichao Sun, Xiaoling Yang, Haibao Jin, Shaoliang Lin","doi":"10.1021/acs.biomac.5c00211","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00211","url":null,"abstract":"Ultrathin organic nanofibers (UTONFs) have favorable potential as emerging nanomaterials due to their large aspect ratio, lightweight nature, and mechanical flexibility. Achieving dual stimuli-responsive UTONFs is necessary to satisfy the on-demand requirements of smart and miniature devices but remains challenging. Herein, amphiphilic alternating peptoids (AAPs) modified with azobenzene and histamine groups were successfully synthesized using the solid-phase submonomer synthesis technique. Following subsequent solution self-assembly, photo/CO2 dual-responsive ultrathin peptoid nanofibers (UTPNFs) with a diameter of ∼1.8 nm and a length of up to several micrometers were generated based on the pendant hydrophobic conjugate stacking mechanism. The photoisomerization of azobenzene was accountable for the reversible transformation from UTPNFs to spherical micelles (∼60 nm) under recyclable light irradiation. Owing to the protonation and the resulting electrostatic repulsion interaction, both UTPNFs and spherical micelles displayed a reversible variation in shape and physicochemical properties, including the size, diameter, zeta potential, and pH. Our work offers prospective guidance on the construction of dual-responsive ultrathin organic nanofibers with controllable shape transformation and performance transition.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727017","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}

引用次数: 0

Lipid-Modified PEI Derivative-Based Binary/Ternary Polyplex Formulations for the Delivery of pDNA and mRNA in Primary Cells.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-27 DOI: 10.1021/acs.biomac.5c00169

Amarnath Praphakar Rajendran, Daniel Nisakar Meenakshi Sundaram, Luis Carlos Morales, Cezary Kucharski, Mohammad Nasrullah, Burcak Bulut, Pavlo Michailo Tsisar, Aislinn D Maguire, Bradley J Kerr, Hasan Uludağ

{"title":"Lipid-Modified PEI Derivative-Based Binary/Ternary Polyplex Formulations for the Delivery of pDNA and mRNA in Primary Cells.","authors":"Amarnath Praphakar Rajendran, Daniel Nisakar Meenakshi Sundaram, Luis Carlos Morales, Cezary Kucharski, Mohammad Nasrullah, Burcak Bulut, Pavlo Michailo Tsisar, Aislinn D Maguire, Bradley J Kerr, Hasan Uludağ","doi":"10.1021/acs.biomac.5c00169","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00169","url":null,"abstract":"A previous study has demonstrated the benefit of modification of polyethylenimine (PEI1.2k) by lipids through a p-hydroxyphenylacetic acid (PHPA) linker and polyanion (PA), which is now extended in this report to several primary cells. The formulated binary (lipopolymer/NAs) and ternary (lipopolymer/NAs/PA) complexes displayed no significant toxicity (MTT/hemolysis assay). The pDNA/mRNA complexes with PEI1.2k-PHPA-Lin9 and PEI1.2k-PHPA-Lau5-Ole5 lipopolymers showed gene expression levels higher than those of other lipopolymers. The transfection efficiencies of the ternary polyplexes of these lipopolymers possessed higher gene expression than those of the binary polyplexes. The serum-stable ternary polyplexes of PEI1.2k-PHPA-Lau5-Ole5 maintained high levels of mRNA expression in the lungs along with the spleen after intravenous injection. As in in vitro studies, transgene expression was relatively weak with binary complexes in muscle; however, a 10-fold higher efficiency was obtained with ternary complexes. Overall, our results provide improved gene formulations for the transfections of primary cells in vitro, as well as in in vivo animal models.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727021","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}

引用次数: 0

Hyperstable and Fibril-Forming Collagen-Mimetic Peptides in Shortest Triple Helices: Empowering the Capping by π-systems.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-27 DOI: 10.1021/acs.biomac.4c01455

Smriti Mukherjee, Vijayakumar Varshashankari, Ancy Feba, Niraikulam Ayyadurai, Kanagasabai Balamurugan, Ganesh Shanmugam

{"title":"Hyperstable and Fibril-Forming Collagen-Mimetic Peptides in Shortest Triple Helices: Empowering the Capping by π-systems.","authors":"Smriti Mukherjee, Vijayakumar Varshashankari, Ancy Feba, Niraikulam Ayyadurai, Kanagasabai Balamurugan, Ganesh Shanmugam","doi":"10.1021/acs.biomac.4c01455","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01455","url":null,"abstract":"Developing collagen-mimetic peptides (CMPs) with short triple helices and fibril-forming ability remains challenging. Herein, we stabilized short CMPs (3-6 GPO repeats) by attaching extended aromatic π-system─fluorenyl groups at the N-terminus and tyrosine at the C-terminus. These modifications promoted triple helix folding through π-π interactions, acting as a \"glue\" to stabilize the structure and facilitate fibrillation. A single fluorenyl cap required 5 GPO repeats for helix formation, while double fluorenyl capping reduced this to 4 repeats. Notably, at pH 5.5, triple helices formed with only 3 GPO repeats. The double-capped CMPs exhibited hyperstability (Tm = 76 °C) and formed fibrillar networks at physiological pH. Biophysical and computational studies confirmed the role of π-π and CH-π interactions, along with hydrogen bonding, in stabilization. The minimalistic CMPs supported cell viability, demonstrating their potential for biomedical applications. This strategy offers a method to design highly stable, short CMPs that form robust fibrillar networks.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727020","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}

引用次数: 0

Bioactive Polymeric Scaffolds: Multivalent Functionalization by Thermal Azide-Alkyne Cycloaddition with Alkynyl Dicarbamates.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-26 DOI: 10.1021/acs.biomac.5c00038

Maun H Tawara, Juan Correa, Emma Leire, Bruno Delgado Gonzalez, Samuel Parcero-Bouzas, Flonja Liko, Eduardo Fernandez-Megia

{"title":"Bioactive Polymeric Scaffolds: Multivalent Functionalization by Thermal Azide-Alkyne Cycloaddition with Alkynyl Dicarbamates.","authors":"Maun H Tawara, Juan Correa, Emma Leire, Bruno Delgado Gonzalez, Samuel Parcero-Bouzas, Flonja Liko, Eduardo Fernandez-Megia","doi":"10.1021/acs.biomac.5c00038","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00038","url":null,"abstract":"Multivalency enables interactions with higher affinities and specificities than monovalent interactions. The strategy exploited by nature to modulate biorecognition has inspired the design of multivalent conjugates with therapeutic properties. However, chemical functionalization often requires coupling agents, additives, or metal catalysts that complicate isolation and purification. Herein, azide-alkyne cycloaddition (AAC) with alkynyl dicarbamates (Alk-R) is presented as a flexible, reliable, atom-economical, and user-friendly strategy for the multivalent functionalization of polymeric scaffolds. Alk-R functionalized with biologically relevant ligands have been prepared and used for the multivalent AAC functionalization of azide-bearing dendrimers and block copolymers. The resulting polymers with double multivalency reveal a platform for the development of bioinspired functional systems with promising applications in drug delivery: block copolymer micelles and multifunctional nanocarriers with synergistically integrated probes-ligands-drugs. The extension of this strategy to other ligands and scaffolds is expected to open up a wide range of therapeutic and diagnostic opportunities.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727016","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}

引用次数: 0

Diboronate-Modified Hyaluronic Acid for Glucose-Responsive Insulin Delivery.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-26 DOI: 10.1021/acs.biomac.5c00144

Sijie Xian, Yuanhui Xiang, Katarína Mitrová, Jiří Jiráček, Matthew J Webber

{"title":"Diboronate-Modified Hyaluronic Acid for Glucose-Responsive Insulin Delivery.","authors":"Sijie Xian, Yuanhui Xiang, Katarína Mitrová, Jiří Jiráček, Matthew J Webber","doi":"10.1021/acs.biomac.5c00144","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00144","url":null,"abstract":"Diabetes requires precise insulin management to maintain glycemic control and prevent severe complications. Glucose-responsive delivery systems envision an autonomous approach to improve insulin therapy. Here, a glucose-sensitive insulin delivery system comprising hyaluronic acid conjugated with a diboronate glucose binder as a carrier for diol-modified insulin is shown. This approach seeks improved precision in insulin delivery, leveraging bidentate glucose binding to achieve enhanced glucose affinity and specificity. Modification of insulin with a diol motif preserves its native conformation and function. These insulin formulations correct blood glucose in diabetic mice, including glucose-responsive function when subjected to a glucose challenge. However, the absence of secondary interactions, such as electrostatic complexation, ultimately limits the duration of function relative to that of previous platforms. Integrating complementary interactions alongside dynamic-covalent glucose binders therefore enhances the functional duration and therapeutic efficacy in the design of glucose-responsive polymeric carriers, offering design insights into the development of new carriers for glucose-responsive insulin delivery.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143717596","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}

引用次数: 0

NO-Releasing Metal-Organic Framework-Based Composite Coatings with Heparin-Mimicking Copolymers on Titanium Substrates: Impact on Vascular Cell Behavior.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-26 DOI: 10.1021/acs.biomac.5c00016

Denghai Sheng, Shuaihang Guo, Aiqing Li, Qiulian Wu, Mengying Zhan, Xiaoli Liu, Hong Chen

引用次数: 0

Enhancing Biodegradable Bone Plate Performance: Stereocomplex Polylactic Acid for Improved Mechanical Properties and Near-Infrared Transparency.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-25 DOI: 10.1021/acs.biomac.4c01768

Su Jeong Park, Ho-Kyung Lim, Sung-Jae Lee, Seung Hyuk Im, Jong Min Lee, Youngmee Jung, Soo Hyun Kim, Ji-Seok Shim, Jong-Eun Won, Justin J Chung, In-Seok Song

{"title":"Enhancing Biodegradable Bone Plate Performance: Stereocomplex Polylactic Acid for Improved Mechanical Properties and Near-Infrared Transparency.","authors":"Su Jeong Park, Ho-Kyung Lim, Sung-Jae Lee, Seung Hyuk Im, Jong Min Lee, Youngmee Jung, Soo Hyun Kim, Ji-Seok Shim, Jong-Eun Won, Justin J Chung, In-Seok Song","doi":"10.1021/acs.biomac.4c01768","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01768","url":null,"abstract":"The use of biodegradable materials in bone plates offers remarkable advantages; however, their application in bone fixation is limited by their brittleness. Moreover, treatments tailored to patient conditions are needed in orthopedics. In this study, bone plates were fabricated with stereocomplex polylactic acid (scPLA) and the effects of poly(d-lactic acid) molecular weight and scPLA blending ratios were analyzed. Although modulus values of poly(l-lactic acid) (PLLA) and scPLA were similar, strain resistance improved at higher scPLA proportions. The enhanced elongation was owing to the presence of tie molecules within the scPLA as opposed to single PLA chains. The fabricated scPLA bone plates exhibited improved mechanical properties and transparency in the optical and near-infrared ranges. scPLA was characterized by a smaller crystallite size. These properties of scPLA combined with its biocompatibility indicate potential for various diagnostic and therapeutic orthopedic applications. Comparisons with commercial PLLA-based bone plates show no significant differences in in vivo bone-healing ability.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699088","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}

引用次数: 0

Improving Complex Coacervate Tissue Adhesive Performance Using Bridging Polymer Chains.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-25 DOI: 10.1021/acs.biomac.4c01801

Ayla N Kwant, Julien S Es Sayed, Nawal Aledlbi, Hanna Pryshchepa, Pieter J van der Zaag, Janette K Burgess, Dirk-Jan Slebos, Simon D Pouwels, Marleen Kamperman

{"title":"Improving Complex Coacervate Tissue Adhesive Performance Using Bridging Polymer Chains.","authors":"Ayla N Kwant, Julien S Es Sayed, Nawal Aledlbi, Hanna Pryshchepa, Pieter J van der Zaag, Janette K Burgess, Dirk-Jan Slebos, Simon D Pouwels, Marleen Kamperman","doi":"10.1021/acs.biomac.4c01801","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01801","url":null,"abstract":"Complex coacervates have emerged as promising tissue adhesives due to their excellent wet adhesion and tunable properties. However, maintaining stable adhesion on soft, dynamic tissues remains challenging. In this study, the use of a bridging polymer was investigated to enhance the adhesive properties of a complex coacervate adhesive (CCA) composed of poly(allylamine hydrochloride) (pAH) and polysulfopropyl methacrylate (pSPMA). The CCA undergoes solidification as a result of a change in salt concentration, forming a robust adhesive under physiological conditions. Pretreatment with pAH, but not pSPMA, significantly improved adhesion energy on both model hydrogels and biological tissues by forming a polymer-rich bridging layer at the interface. The beneficial effect was driven by accumulation of pAH in superficial layers of both the CCA and the substrates. This enabled the CCA to withstand higher deformation before adhesive failure. These findings underscore the potential of bridging polymers to improve CCAs and other tissue adhesives for biomedical applications.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699089","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}

引用次数: 0

Insights into Protein Unfolding under pH, Temperature, and Shear Using Molecular Dynamics Simulations.

IF 5.5 2区化学

Biomacromolecules Pub Date : 2025-03-25 DOI: 10.1021/acs.biomac.4c00991

Yinhao Jia, Clare Cocker, Janani Sampath

{"title":"Insights into Protein Unfolding under pH, Temperature, and Shear Using Molecular Dynamics Simulations.","authors":"Yinhao Jia, Clare Cocker, Janani Sampath","doi":"10.1021/acs.biomac.4c00991","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c00991","url":null,"abstract":"Protein biologics hold immense potential in therapeutic applications, but their ephemeral nature has hindered widespread application. The effects of different stressors on protein folding have long been studied, but whether these stressors induce protein unfolding through different pathways remains unclear. Here, we conduct all-atom molecular dynamics simulations to investigate the unfolding of bovine serum albumin (BSA) under three distinct stressors: high temperature, acidic pH, and shear stress. Our findings reveal that each stressor induces unique unfolding patterns in BSA, indicating stressor-specific unfolding pathways. Structural analyses show that high temperature significantly disrupts the protein's secondary structure, while acidic pH causes alternations in the tertiary structure, leading to domain separation. Shear stress initially perturbs the tertiary structure, initiating structural rearrangements, which causes a loss of secondary structure similar to temperature. These distinct unfolding behaviors suggest that different stabilization strategies are required to enhance protein stability under different denaturation conditions.","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699090","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}

引用次数: 0