{"title":"Dynamic covalent bond-based materials: From construction to biomedical applications","authors":"Banruo Xianyu, Huaping Xu","doi":"10.1016/j.supmat.2024.100070","DOIUrl":"10.1016/j.supmat.2024.100070","url":null,"abstract":"<div><p>Dynamic covalent bonds (DCBs) have received significant interest due to their unique reversibility and stimuli-responsiveness. The introduction of DCBs provides materials with self-healing and controllable load and release properties, which result in the emergence of widespread applications in biomedical disciplines. In this minireview, we first introduce the chemistry nature and reaction characteristics of different types of DCBs followed by discussing the design strategies of DCB materials. Finally, we summarize the latest progress about the biomedical applications, including drug delivery, enzyme regulation, molecule recognition and detection, wound healing, biosensing and cell culture, and propose some challenges in the future development of DCB biomaterials.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100070"},"PeriodicalIF":0.0,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000084/pdfft?md5=09c15973cbab55ad9c6668c78b2e19e9&pid=1-s2.0-S2667240524000084-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140760550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Hydrogen-bonding induced assembly of polymer-grafted nanoparticles towards photothermal antibacterial activities","authors":"Simeng Liu, Zhuo-Ran Yang, Yinhan Xu, Mengmeng Zhang, Hao Jiang, Jiangping Xu, Jintao Zhu","doi":"10.1016/j.supmat.2024.100069","DOIUrl":"https://doi.org/10.1016/j.supmat.2024.100069","url":null,"abstract":"<div><p>The multiple hydrogen-bond has been introduced as a reversible driving force for directing the assembly of polymer-grafted nanoparticles (PGNPs). The complementary hydrogen-bonds among the polymer ligands lead to the spontaneous aggregation of PGNPs. However, it may also induce the uncontrollable aggregation of PGNPs into assemblies with non-uniform size, even irregular precipitates, due to the immoderate agglomeration associated with the strong interactions of multiple hydrogen-bonds. This severely limits the stable dispersion of PGNP aggregates in a solvent and their applications. In this work, the gold nanoparticles (AuNPs) grafted with thymine-terminated polystyrene (AuNP@PS-Thy) and diaminopyridine-terminated polystyrene (AuNP@PS-Dap) were synthesized, respectively. Their thermal-responsive assembly behavior in an organic solvent was systematically studied. By optimizing the assembly conditions, i.e., the concentration of PGNPs and the incubation time, the assemblies of AuNP@PS-Thy/AuNP@PS-Dap with controllable size were obtained. Interestingly, the assemblies deposited on a solid substrate showed excellent photothermal antimicrobial activities under irradiation of 808 nm and 655 nm lasers. The killing percentage of <em>Staphylococcus aureus (S. aureus)</em> and <em>Escherichia coli</em> (<em>E. coli</em>) could reach 99 % after irradiating for 10 min. This work establishes an approach for controlling the hydrogen-bonding-induced assembly behavior of PGNPs, which may be extended to construct functional metamaterials with controllable structures.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100069"},"PeriodicalIF":0.0,"publicationDate":"2024-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000072/pdfft?md5=8d348ae76cfde10c4a8f5996efa47893&pid=1-s2.0-S2667240524000072-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140550977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuyue Zhao , Bingqiang Li , Yiqing Song , Shian Wu , Haodong Hu , Jianzu Wang , Linqi Shi , Fan Huang
{"title":"Temperature-responsive self-assembly Nanochaperone protects Green Fluorescent Proteins from Thermal denaturation","authors":"Shuyue Zhao , Bingqiang Li , Yiqing Song , Shian Wu , Haodong Hu , Jianzu Wang , Linqi Shi , Fan Huang","doi":"10.1016/j.supmat.2024.100067","DOIUrl":"10.1016/j.supmat.2024.100067","url":null,"abstract":"<div><p>Protein products perform important roles in the biochemistry field, but the thermal inactivation of proteins will increase the difficulty of their transport, storage and application. Therefore, improving the thermal stability of proteins has become a thorny challenge. Natural molecular chaperones can efficiently improve the resistance of proteins to environmental stimuli by reversible supramolecular assembly with proteins. Inspired by this machine, herein we designed a nanochaperone (nChap) with thermo-responsive amphiphilic surfaces that can prevent thermal denaturation and facilitate refolding of green fluorescent proteins (GFPs). By mimicking the hydrophobic microregion of natural chaperones, this nChap can effectively capture free GFPs and hide them into surface confined spaces, thereby shielding exposed hydrophobic sites of GFPs and preventing their irreversible thermal aggregation. When the heat stimulation disappeared, the thermosensitive segments of the nChaps underwent the hydrophilic transition, which provided suitable microenvironments for GFPs refolding. More importantly, nChaps could also actively adsorb to the surface of immobilized GFPs at high temperatures and realize the satisfactory dissociation of the nChap-protein complex upon cooling, which exhibited excellent chaperone-like activity. This work provides significant insights for understanding and developing strategies to improve protein stability.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100067"},"PeriodicalIF":0.0,"publicationDate":"2024-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000059/pdfft?md5=c3e7a871d96142301ea8358dad305bae&pid=1-s2.0-S2667240524000059-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140404672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wei Ma , Bin Wang , Dun Wang, Ying Liu, Ming-Chao Jiang, Jin-Yan Zhang, Dong-Dong Peng, Zhi-Cheng Li, Cui-Yun Yu, Hua Wei
{"title":"A self-cascade terpolymer platform for amplified chemo-chemodynamic therapy with synergistic immunogenic cell death enhancement","authors":"Wei Ma , Bin Wang , Dun Wang, Ying Liu, Ming-Chao Jiang, Jin-Yan Zhang, Dong-Dong Peng, Zhi-Cheng Li, Cui-Yun Yu, Hua Wei","doi":"10.1016/j.supmat.2024.100066","DOIUrl":"10.1016/j.supmat.2024.100066","url":null,"abstract":"<div><p>Chemodynamic therapy, which relies on the generation of cytotoxic radicals, can be amplified by a nanoplatform that produces hydroxyl radicals while also compromising natural radical scavenging mechanisms. For this purpose, a well-defined amphiphilic terpolymer, poly(oligo(ethylene glycol) monomethyl ether methacrylate)-<em>block</em>-poly(<em>N,N</em>-dimethyl aminoethyl methacrylate-<em>statistical</em>-monomer bearing ferrocene graft via azobenzene linker) (POEGMA-<em>b</em>-P(DMAEMA-<em>st</em>-(M-Azo-Fc), denoted as PAzo-Fc) is prepared by a consecutive reversible addition-fragmentation chain transfer (RAFT) polymerization technique, and is further used for doxorubicin (DOX) encapsulation to afford DOX-loaded stabilized nanomicelles, DOX@PAzo-Fc with an average hydrodynamic diameter of 86.0 nm. DOX@PAzo-Fc shows a self-cascade property for amplified CDT. That is, Azo cleavage-induced glutathione (GSH) depletion alleviates reactive oxygen species (ROS) scavenging. Together with the DOX-enhanced hydrogen peroxide generation, the Fc-mediated Fenton reaction is boosted for enhanced CDT. More importantly, the resulting amplified cascade chemo-chemodynamic therapy exerts a synergistic immunogenic cell death (ICD) enhancement effect for effective cancer immunotherapy, which further resulted in a high tumor inhibition rate of 87.8 % in murine tumor models. The uniqueness of this study is the construction of a minimalist nanoplatform based on M-Azo-Fc units for amplified CDT via simultaneously producing hydroxyl radicals and compromising natural radical scavenging mechanisms. Overall, this self-cascade terpolymer platform fabricated herein offers a facile yet robust approach for advanced combinatory cancer therapy with great potential for clinical translations.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100066"},"PeriodicalIF":0.0,"publicationDate":"2024-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000047/pdfft?md5=ddf8de3d31f9d1c7720483df2f1a5b66&pid=1-s2.0-S2667240524000047-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140269642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A visualizable strategy to real-time monitor chiral block copolypeptide assembly by AIE fluorescent probes","authors":"Zenghao Li, Yanan Liu, Jing Sun","doi":"10.1016/j.supmat.2024.100065","DOIUrl":"10.1016/j.supmat.2024.100065","url":null,"abstract":"<div><p>Aggregation-induced emission (AIE) luminogens show great potential in many applications. In this study, we have synthesized diblock copolymers poly (ethylene glycol) -<em>b</em>-poly (9-anthrylmethyl-<sub>L</sub>-lysine) (PEG-<em>b</em>-PLLys-An) and poly (ethylene glycol) -<em>b</em>-poly (9-anthrylmethyl-<sub>D</sub>-lysine) PEG-<em>b</em>-PDLys-An with opposite handedness by ring-opening polymerization and post-modification. Both diblock copolymers can self-assemble into spherical micelles or planar connected disc-like aggregates at different water fractions. In addition, the copolymers present a typical AIE process concomitant with the self-assembly process. To facilitate the study of chain exchange kinetics, we develope a novel visualizable strategy based on fluorescence variation. This strategy allows us to monitor the real-time chain exchange process by mixing equimolar solutions of PEG<sub>44</sub>-<em>b</em>-PDLys<sub>20</sub>-An and PEG<sub>44</sub>-<em>b</em>-PLLys<sub>20</sub>-An with varying water volume fractions. We indicate that chain exchange predominantly occurs at low water fractions through a single-molecule extraction and redistribution mechanism rather than micellar fission and fusion. In contrast, the micelles appear to be \"kinetically frozen\" at high water fractions, suggesting suppressed chain exchange under these conditions. Importantly, our approach offers a visually observable method for probing the dynamics of micellar chain exchange in real time.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100065"},"PeriodicalIF":0.0,"publicationDate":"2024-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000035/pdfft?md5=6d368e2e265b9d94493de84937e96968&pid=1-s2.0-S2667240524000035-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139637634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Supramolecular fluorescence biosensing based on macrocycles","authors":"Jia-Hong Tian , Haiqi Xu , Xin-Yue Hu , Dong-Sheng Guo","doi":"10.1016/j.supmat.2024.100063","DOIUrl":"https://doi.org/10.1016/j.supmat.2024.100063","url":null,"abstract":"<div><p>Fluorescence sensing converts chemical events into measurable readings by utilizing fluorescence signals for the qualitative or quantitative detection of specific analytes. Supramolecular chemistry, reliant upon non-covalent interactions, has emerged as a potent paradigm for sensing applications, garnering significant scholarly attention. The adoption of supramolecular chemistry within the realm of sensing offers several significant advantages, including easy construction, rapid response, dynamic reversibility, and compatibility with pattern recognition. Notably, molecular recognition stands as a pivotal facet of supramolecular sensing. Among the integral constituents of supramolecular chemistry, an array of macrocyclic compounds boasts remarkable molecular recognition properties, apt for diverse guest molecules, and finds extensive utility in fluorescence sensing. This review highlights the pivotal contributions of fluorescent sensors rooted in crown ethers, cyclodextrins, calixarenes, cucurbiturils, and other macrocycles in single sensing, differential sensing and bioimaging. The versatility of these sensors extends to diverse media, encompassing aqueous environments, buffer solutions, and biofluid matrices. Additionally, this review provides insights into the future endeavors and forthcoming research directions in the field of supramolecular sensing and imaging.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100063"},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000011/pdfft?md5=96dd51e2b7aed59928f49fce30504427&pid=1-s2.0-S2667240524000011-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139549813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Supramolecular co-assembled hybrid hydrogels for antibacterial therapy","authors":"Zakia Riaz, Sravan Baddi, Chuan-Liang Feng","doi":"10.1016/j.supmat.2024.100064","DOIUrl":"https://doi.org/10.1016/j.supmat.2024.100064","url":null,"abstract":"<div><p>Bacterial infections arising from antibiotic-resistant strains represent a formidable global health threat. In the realm of antibacterial therapies, supramolecular hydrogels stand out with unique advantages owing to their adaptable and flexible non-covalent interactions with diverse biomolecules. Their ability to encapsulate a variety of biologically active agents through co-assembly further amplifies their efficacy, endowing these hybrid hydrogels with a spectrum of functionalities within a unified system. Various functionalities encompass self-healing, injectability, tissue adhesion, facile drug loading, controlled release mechanisms, biocompatibility, antibacterial properties, and antioxidative attributes. This review article delves into two categories of supramolecular antibacterial hydrogels: i) those with intrinsic antibacterial attributes and ii) supramolecular co-assembled hybrid hydrogels formed through the integration of hydrogels with an assortment of active antibacterial agents, including various nanomaterials, antibiotics, biologically active compounds derived from natural sources, and antibacterial polymers. The anticipated role of supramolecular co-assembled hybrid hydrogels, coupled with contemporary medical technologies and devices, is paramount in the development of highly effective and secure platforms for antibacterial therapy. Furthermore, review addresses the current challenges in the realm of antibacterial hydrogels while elucidating prospective future advancements in this field.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100064"},"PeriodicalIF":0.0,"publicationDate":"2024-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240524000023/pdfft?md5=95b9b2dcb3b390f7bc0192229cbcbd14&pid=1-s2.0-S2667240524000023-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139487577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fabrication of the polyetherketoneketone-reinforced nano-hydroxyapatite composites as inspired by the cortical bone","authors":"Zhongyi Wang , Yadong Zhang , Junyi Zhao , Chenyang Xie , Qiang Wei , Haiyang Yu","doi":"10.1016/j.supmat.2023.100062","DOIUrl":"10.1016/j.supmat.2023.100062","url":null,"abstract":"<div><p>Cortical bone has superior mechanical performance. Hydroxyapatite (HA) as its main component are attractive bioactive materials, but possess weak strength. The critical factor is the difference in the structure. Inspired by the hierarchical and delicate architecture of the cortical bone, we used a slurry with 2 wt% polyvinyl alcohol (PVA) and 20 vol% polydopamine-modified nano HA (nHA, pDA-nHA) to fabricate stronger scaffolds characterized by a lamellar structure. Additionally, we immersed the pDA-nHA scaffolds into the polyetherketoneketone (PEKK) synthesis system to reinforce the scaffolds. The cortical bone-inspired composites were produced successfully, and the 20 vol% pDA-nHA+2 wt% PVA/PEKK composites had the highest strength and modulus. It provides a new solution for enhancing the mechanical strength of the single component, as well as improving the bioactivity of PEKK.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100062"},"PeriodicalIF":0.0,"publicationDate":"2024-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240523000326/pdfft?md5=04b9f88785421cf4df6b38173b314114&pid=1-s2.0-S2667240523000326-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139539975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Exploring water−macromolecule interactions at the single-molecule level: A comprehensive review","authors":"Yixuan Shan, Yu Bao, Shuxun Cui","doi":"10.1016/j.supmat.2023.100061","DOIUrl":"10.1016/j.supmat.2023.100061","url":null,"abstract":"<div><p>Water is ubiquitous and indispensable on the Earth. Its importance has long been recognized on a macroscopic scale. However, it took a long time to comprehend the impact of water molecules on the microscopic level. According to the hydrophilicity of matter, the impact of water can be divided into two categories: 1) intermolecular hydrogen bonds (H-bonds) and 2) hydrophobic interactions. In recent years, atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) has been used to investigate the effect of water on the single-chain properties of macromolecules. Herein, we summarize recent advances in the AFM-SMFS study on the impact of water on some kinds of synthetic polymers, biomacromolecules, and molecules containing supramolecular interactions from the two aspects of H-bonds and hydrophobic interactions. It is expected that a deeper understanding of the interactions between water molecules and macromolecules will enable the design of polymer materials with specific functionalities and properties in a bottom-up way.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100061"},"PeriodicalIF":0.0,"publicationDate":"2024-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240523000314/pdfft?md5=0a49d7258c0ed0b849bfad78d9d3838e&pid=1-s2.0-S2667240523000314-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139392343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Mechanically Interlocked Biomacromolecules","authors":"Yu-Xiang Wang, Wen-Hao Wu, Feng-Yi Jiang, Wen-Bin Zhang","doi":"10.1016/j.supmat.2023.100059","DOIUrl":"10.1016/j.supmat.2023.100059","url":null,"abstract":"<div><p>Mechanical interlocking is a prominent phenomenon both in macroscopic objects and in microscopic molecules. Not only is it aesthetically appealing, it also leads to unique properties such as extraordinary mechanical stability. This review focuses on mechanically interlocked biomacromolecules. After a brief clarification on the concept and scope, we discuss their classification and summarize the three main types of mechanically interlocked biomacromolecules (i.e., DNA, RNA, and proteins) in terms of their natural occurrence, synthetic methods, relevant applications, and functional benefits. It has been found that mechanical interlocking reshapes the conformational space of these chain molecules, which provides numerous opportunities to tailor their properties and create new functions. Since the development of \"assembly-reaction\" synergies has greatly facilitated their synthetic availability, these mechanically linked biomacromolecules will become unique and promising candidates for various applications in biomaterials and biomedicine.</p></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"3 ","pages":"Article 100059"},"PeriodicalIF":0.0,"publicationDate":"2023-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2667240523000296/pdfft?md5=5109bb992b4a35375e12f6d3516f2eac&pid=1-s2.0-S2667240523000296-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138993769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}