Chun-Wei Chang, Bronwin L. Dargaville, Konstantin I. Momot, Dietmar W. Hutmacher
{"title":"19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels","authors":"Chun-Wei Chang, Bronwin L. Dargaville, Konstantin I. Momot, Dietmar W. Hutmacher","doi":"10.1002/mame.202400348","DOIUrl":"https://doi.org/10.1002/mame.202400348","url":null,"abstract":"<p>Understanding payload diffusion is an important topic in hydrogel drug delivery. While proton nuclear magnetic resonance (NMR) spectroscopy allows for direct examination of water dynamics in hydrogels, it is challenging to study the dynamics of payloads due to spectral crowding and distortions. Fluorine-19, not biologically endogenous in humans and having high NMR receptivity, can be easily incorporated into molecules of interest and therefore used as an alternative probe for dynamics of payload molecules in hydrogels. In this study, the dynamics of fluorine-containing compounds trifluoroethylamine (TFEA, a small molecule), ciprofloxacin (CF, a medium-size molecule), and fluorinated lysozyme (FL, a ≈15 kDa protein) are measured both in solution and gelatin methacrylate (GelMA) hydrogels. For each payload molecule, the rotational correlation time and translational diffusion coefficient, as well as the effective microviscosity of the media, are measured. Spin-spin relaxation (T<sub>2</sub>) is also used to probe chemical exchange as an indicator of payload–polymer interactions. The in situ interaction between payload and polymer network and precise characterization of payload dynamics within hydrogels show that fluorine-19 nuclear magnetic resonance (<sup>19</sup>F NMR) relaxometry and diffusometry are important techniques in hydrogel drug delivery and, more generally, in biomaterial science, tissue engineering, and regenerative medicine.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 8","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202400348","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144869329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Nanomaterial-Integrated 3D Biofabricated Structures for Advanced Biomedical Applications","authors":"Mustafijur Rahman, Tanvir Mahady Dip, Md Golam Nur, Md Hasibul Hossain, Finn Snow, Nusrat Binta Hossain, Azadeh Mirabedini, Anita Quigley, Rajiv Padhye, Shadi Houshyar","doi":"10.1002/mame.202500083","DOIUrl":"https://doi.org/10.1002/mame.202500083","url":null,"abstract":"<p>In recent times, the integration of nanomaterials into 3D biofabricated structures has become a transformative approach in advancing the biomedical field. Nanomaterials exhibit distinctive properties such as superior mechanical strength, enhanced biocompatibility, and improved drug delivery efficiency, making them well-suited for biomedical use. This comprehensive review explores the synergistic potential of combining nanomaterials—such as metallic, carbon-based, ceramic, and polymeric nanoparticles—with advanced 3D biofabrication techniques, including 3D bioprinting, melt electrowriting, and electrospinning. These integrations have demonstrated significant promise in diverse biomedical applications, such as regeneration of nerve, bone, and cardiac tissues, wound healing, and cancer therapy. Despite substantial progress, several challenges hinder clinical translation, including difficulties in achieving precise nanomaterial integration, biocompatibility and toxicity concerns, scalability in manufacturing, and regulatory complexities. This review synthesizes recent advancements, evaluates existing challenges, and identifies key research directions to address these obstacles. It highlights the significance of interdisciplinary collaboration in maximizing the potential of nanomaterial-integrated 3D biofabricated structures and promoting innovative advancements in biomedical science and healthcare.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 8","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500083","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144869328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Weiqing Fang, Mark Duncan, Mahima Dua, Pierre Mertiny, Hani E. Naguib
{"title":"Machine Learning-Assisted Design of Multilayer Thermoplastic Composites: Robust Neural Network Prediction and Feature Importance Analysis","authors":"Weiqing Fang, Mark Duncan, Mahima Dua, Pierre Mertiny, Hani E. Naguib","doi":"10.1002/mame.202500093","DOIUrl":"https://doi.org/10.1002/mame.202500093","url":null,"abstract":"<p>Multilayer thermoplastic composites offer sustainable alternatives to traditional thermoset and metal materials. However, their design is inherently complex, involving numerous interdependent parameters that render conventional processes both expensive and time-consuming. While machine learning-assisted methods provide a potential solution, they typically require large datasets that can be costly to obtain. This study explores a robust neural network, specifically, an Advanced Multilayer Perceptron (AdvMLP) Regressor, to predict the peel strength of multilayer thermoplastic composites. Through architectural enhancements, the AdvMLP is effectively trained on a limited yet authentic manufacturing dataset, yielding robust predictions validated by benchmark metrics and k-fold cross-validation. The model captures the intricate interplay between manufacturing processes and composite properties, enabling comprehensive feature importance analysis and dimensionality reduction. Overall, this study establishes a robust and generalizable machine learning-assisted methodology to guide and accelerate the design and optimization of multilayer thermoplastic composites.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 9","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500093","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Correction to “Conductive Open-Cell Silicone Foam for Tunable Damping and Impact Sensing Application”","authors":"","doi":"10.1002/mame.70017","DOIUrl":"https://doi.org/10.1002/mame.70017","url":null,"abstract":"<p>[Conductive Open-Cell Silicone Foam for Tunable Damping and Impact Sensing Application</p><p>Rene Preuer, Jan Sleichrt, Daniel Kytyr, Philip Lindner, Umut Cakmak, Ingrid Graz</p><p><i>Macromol. Mater. Eng</i>. <b>2025</b>, <i>310</i>, 2400273]</p><p>https://doi.org/10.1002/mame.202400273</p><p>The funding statement for this article was missing. The below funding statement has been added to the article:</p><p>Open Access funding provided by Johannes Kepler Universität Linz/KEMÖ</p><p>We apologize for this error.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 5","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.70017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hatice Hande Mert, Betül Şebnem Şimşiroğlu, Elif Nur Özer, Hülya Çelik-Onar, Jülide Hizal, Mehmet Selçuk Mert
{"title":"Lauric Acid Based Composite Phase Change Materials Form-Stabilized with Highly Crosslinked Polymer for Thermal Energy Storage","authors":"Hatice Hande Mert, Betül Şebnem Şimşiroğlu, Elif Nur Özer, Hülya Çelik-Onar, Jülide Hizal, Mehmet Selçuk Mert","doi":"10.1002/mame.202500111","DOIUrl":"https://doi.org/10.1002/mame.202500111","url":null,"abstract":"<p>Lauric acid (LA)-based composite phase change materials (PCMs) are prepared using a novel porous highly crosslinked polymer (HCP) framework synthesized from coumarin-3-carboxamide derived material via the Friedel-Crafts alkylation method. The preparation process of the composite PCMs occurred in three consecutive steps: synthesis of coumarin-3-carboxamide derivative material from coumarin-3-carboxylic acid; synthesis of HCP as support material, and integration of LA into the support matrix through the solvent assisted vacuum absorption process. Form-stabilization of LA with this method is rapid and easy, as well as not requiring extra purification and cleaning for composites compared to production by microencapsulation method. In addition, the advantage of HCP as a PCM support material is due to its appropriate pore morphology, and specific surface area (76.26 m<sup>2</sup> g<sup>−1</sup>). The chemical structure and porous morphology of HCP matrix are detected by Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) analysis, respectively. According to the leakage test performed among the prepared composite PCMs, the LA/HCP-6040 composite containing 60% LA-40% HCP is determined as the composite with the highest ratio of PCM by mass without any leakage. The composite PCMs supported with HCP matrix displayed good thermal stability as a result of thermogravimetric analysis, in addition to thermal energy storage characteristics confirmed by thermal camera views.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 9","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500111","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luigi Botta, Maria Chiara Mistretta, Vincenzo Titone, Silvia Russello, Giuliana Garofalo, Raimondo Gaglio
{"title":"Tuning Antibacterial and Physical Properties of Biodegradable Polymer Systems Incorporating Carvacrol","authors":"Luigi Botta, Maria Chiara Mistretta, Vincenzo Titone, Silvia Russello, Giuliana Garofalo, Raimondo Gaglio","doi":"10.1002/mame.202500013","DOIUrl":"https://doi.org/10.1002/mame.202500013","url":null,"abstract":"<p>The addition of antimicrobial additives in packaging systems is becoming essential, and this study aimed to incorporate carvacrol (CRV) into Poly(lactic acid) (PLA)/Poly(butylene adipate-co-terephthalate) (PBAT) blends to investigate the effects of blend composition on the resulting material's properties, with a particular focus on CRV release kinetics and antibacterial activity. The materials are prepared via melt mixing and compression molding and are thoroughly characterized through mechanical, rheological, and wettability analyses. Tensile tests reveal that adding PBAT to PLA increases flexibility, reducing modulus by 26% and tensile strength by 60%, while elongation at break rises by 550%. Adding PLA to PBAT increases stiffness, with modulus rising by 128%, but tensile strength and elongation decrease by 62% and 70%, respectively. The CRV release profile revealed that the release rate can be modulated by altering the blend composition. In vitro evaluation of antibacterial activity shows that the polymers with high PBAT content and containing CRV inhibited the growth of <i>Listeria monocytogenes</i> to undetectable levels (<1 Log CFU mL<sup>−1</sup>). Overall, the results show that the blend formulation significantly influenced the material properties compared to the pure components, providing effective antibacterial activity against both pathogens.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 9","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"4D Printing of Thermoresponsive OEGMA-Based Hydrogels with Tunable Response","authors":"H. B. Duc Tran, Christoph A. Spiegel, Eva Blasco","doi":"10.1002/mame.202500096","DOIUrl":"https://doi.org/10.1002/mame.202500096","url":null,"abstract":"<p>Hydrogels, particularly those exhibiting responsive behaviors, have gained significant attention, especially with the advent of 4D printing. Among thermoresponsive hydrogels, poly(<i>N</i>-isopropylacrylamide) (PNIPAM)-based materials remain a benchmark for 4D microprinting, featuring typical lower critical solution temperatures (LCSTs) ranging from 32 to 37 °C. However, precise tuning of the LCST to a broader temperature range is necessary to expand the application window. This study introduces thermoresponsive poly(oligo(ethylene glycol)methacrylate) (POEGMA)-based polymers as alternative materials for two-photon laser printing (2PLP). First, a library of prepolymers with LCSTs ranging from 33 to 66 °C is synthesized and characterized. By formulating these prepolymers with a suitable photoinitiator in water, inks compatible with 2PLP are created. The printing performance of each ink is evaluated by fabricating complex 4D microstructures, including various platonic solids exhibiting LCSTs ranging from 33 to 66 °C, surpassing the constraints of PNIPAM. The actuation performance of each material is evaluated quantitatively by monitoring volume changes at different temperatures. Finally, arrays of “twistable” tetrahedrons are fabricated employing the designed materials, showcasing temperature-selective actuation. Thus, it is demonstrated that the careful design of the macromolecular architecture offers precise LCST adjustment in final printed microstructures, a feature highly beneficial for applications like soft microrobotics among others.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 9","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Angela Marotta, Fabio Scherillo, Giovanni Filippone, Martina Salzano de Luna, Veronica Ambrogi
{"title":"Self-healing Coatings Based on Epoxy Vitrimers","authors":"Angela Marotta, Fabio Scherillo, Giovanni Filippone, Martina Salzano de Luna, Veronica Ambrogi","doi":"10.1002/mame.202500005","DOIUrl":"https://doi.org/10.1002/mame.202500005","url":null,"abstract":"<p>The present study focuses on the development of epoxy-based vitrimeric coatings with thermal-healing ability. For this purpose, ethylene glycol diglycidyl ether (EG) is crosslinked with methyl nadic anhydride (MNA) in the presence of 1-methylimidazole (1-MI) as initiator. The heat-induced reprocessability enabled by transesterification-based bond exchange reactions is evaluated by stress relaxation tests as a function of the epoxide/anhydride ratio and the addition of a transesterification catalyst, namely triazobicyclodecene (TBD). The results show that the relaxation process can be accelerated by both TBD and epoxy excess. Furthermore, due to their low viscosity values, the epoxy-based formulations can be easily applied to the substrate using standard deposition techniques and without the aid of solvents or high temperatures. Therefore, the produced epoxy vitrimers are able to provide extended service life while maintaining good protective performance and self-repairability, opening up possibilities for large-scale applications as coatings.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 8","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saul Utrera-Barrios, Liyun Yu, Anne Ladegaard Skov
{"title":"Revisiting the Thermal Transitions of Polydimethylsiloxane (PDMS) Elastomers: Addressing Common Misconceptions with Comprehensive Data","authors":"Saul Utrera-Barrios, Liyun Yu, Anne Ladegaard Skov","doi":"10.1002/mame.202500075","DOIUrl":"https://doi.org/10.1002/mame.202500075","url":null,"abstract":"<p>An important characteristic of silicone elastomers is their ability to maintain their properties over a wide temperature range. This results from the Si─O bond's high flexibility and thermal stability, causing a very low glass transition temperature (Tg) and a high degradation temperature (Td), respectively. However, other thermal transitions, such as crystallization (Tc), cold crystallization (Tcc), and melting (Tm), must also be considered to ensure the elastomers’ optimal performance and use. This study addresses the misconceptions surrounding the assignment of these transition temperatures for the most prevalent type of silicone elastomer, namely polydimethylsiloxane (PDMS) elastomers. The article focuses on rectifying these misunderstandings, particularly in the context of high-tech applications, including aerospace, automotive, coatings, and soft robotics. A diverse range of 15 types of silicones are meticulously analyzed, including elastomers, adhesives, and oils, using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). This study highlights these transition temperatures’ role in shaping silicone elastomers’ thermomechanical behavior and their significance for effective utilization in advanced applications.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 8","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jasmin Pfleger, Dieter Nees, Barbara Stadlober, Anna Maria Coclite
{"title":"Anti-Sticking Coatings for Imprint Tools Prepared by Initiated Chemical Vapor Deposition","authors":"Jasmin Pfleger, Dieter Nees, Barbara Stadlober, Anna Maria Coclite","doi":"10.1002/mame.202500095","DOIUrl":"https://doi.org/10.1002/mame.202500095","url":null,"abstract":"<p>Anti-sticking coatings are an integral part of imprint processes since they facilitate an effortless and defect-free demolding of stamp and imprint. A low surface energy is important for an easy and clean removal of the stamp from the imprint and for enabling a long lifetime of the expensive stamp, whereas conformality of the anti-sticking coating is important to preserve the designed structure dimensions (aspect ratio, critical dimensions, pitch size, etc.). Within this paper a branched perfluoro polyether acrylate monomer is polymerized for the first time by initiated chemical vapor deposition (iCVD) leading to a highly efficient anti-sticking coating. In appropriate conditions, iCVD can produce thin conformal polymer coatings whose mechanical and chemical stability can be significantly improved by tuning the cross-linking density. The coating is furthermore grafted by covalent bonds via a self-assembled monolayer onto the substrate – i.e., the nickel stamp – in order to prevent delamination. As a result, the coating delivers a water contact angle of 109°, more than 80° higher than for the uncoated and cleaned Ni-sample, i.e. 73% WCA reduction, and more than 50° higher than for the uncleaned Ni sample that is stored at ambient condition (i.e. 46% WCA reduction). Long-term imprint tests confirm the durability of the anti-sticking property on the Ni-stamp.</p>","PeriodicalId":18151,"journal":{"name":"Macromolecular Materials and Engineering","volume":"310 8","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mame.202500095","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144869637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}