Soft Matter最新文献

{"title":"Protein-polyelectrolyte complexation: effects of sterically repulsive groups, macromolecular architecture and hierarchical assembly.","authors":"Raman Hlushko, Alexander Marin, Alexander K Andrianov","doi":"10.1039/d4sm01254b","DOIUrl":"https://doi.org/10.1039/d4sm01254b","url":null,"abstract":"<p><p>Self-assembly of proteins and polyelectrolytes in aqueous solutions is a promising approach for the development of advanced biotherapeutics and engineering efficient biotechnological processes. Synthetic polyions containing sterically repulsive ethylene oxide moieties are especially attractive as protein modifying agents, as they can potentially induce a PEGylation-like stabilizing effect without the need for complex covalent binding reactions. In this study, we investigated the protein-binding properties of anionic polyelectrolytes based on an inorganic polyphosphazene backbone, with ethylene oxide groups incorporated into both grafted and linear macromolecular topologies. The study was conducted in aqueous solutions using isothermal titration calorimetry, dynamic light scattering, and cryogenic electron microscopy to analyze the samples in their vitrified state. Our findings revealed that the stability of the resulting protein-polyion complexes and the thermodynamic profiles of these interactions were influenced by the molecular architecture of the polyions. Furthermore, the formation of hierarchical assemblies of polyions, through ionic crosslinking into nanogels, rapidly reduced or eliminated the ability of the polyelectrolyte to bind proteins. The comprehensive analysis, combining thermodynamic, spectroscopy and direct visualization techniques, provides valuable insights into the multivalent charge-charge interactions that are critical for the development of successful non-covalent protein modification methods.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interplay of chain dynamics and ion transport on mechanical behavior and conductivity in ionogels.","authors":"Mengze Lu, Wei Zhen Lian, Zhenhua Xiao, Lu Liu, Zhiwei Fan, Xiaolin Jin, Chuanxia Jiang, Qian Chen, Zheng-Hai Tang, Panchao Yin, Taolin Sun","doi":"10.1039/d4sm01251h","DOIUrl":"https://doi.org/10.1039/d4sm01251h","url":null,"abstract":"<p><p>Understanding the interplay among the mechanical behavior, ionic conductivity and chain dynamics of ionogels is essential for designing flexible conductors that exhibit both high conductivity and excellent mechanical properties. In this study, ionogels were synthesized <i>via</i> the radical polymerization of <i>N</i>,<i>N</i>'-dimethylacrylamide (DMAA) and methacrylic acid (MAAc) monomers in the presence of ionic liquid 1-ethyl-3-methylimidazolium trifluoromethane sulfonate ([EMIM][OTf]). By varying the mass content of ionic liquid within ionogels, we investigated the mechanical behavior and ionic conductivity at the macroscopic scale using tensile, rheological testing and electrochemical impedance spectroscopy, as well as the dynamic behavior of chain segments and ions within the network at the microscopic scale using broadband dielectric relaxation spectroscopy (BDS) over a broad temperature range. Our findings revealed that variations in ionic liquid concentration significantly affect mechanical performance, ionic conductivity, complex conductivity spectra, and complex permittivity spectra. These ionogels exhibited remarkable stretchability, adhesion, and strain-sensing capabilities. Analysis of BDS indicated that the temperature dependence of the hopping frequency (<i>ω</i>_H), the conductivity of free ions (<i>σ</i>_dc), and the relaxation time (<i>τ</i>_s) of chain segments conforms to the Vogel-Tammann-Fulcher (VTF) equation for ionogels with varying ionic liquid content. By correlating <i>τ</i>_s measured through rheological tests and BDS, we observed a transition from Arrhenius to VTF behavior, which shifts towards lower temperatures with increasing ionic liquid content. This study highlighted a strong coupling between <i>σ</i>_dc and <i>ω</i>_H, as well as between 1/<i>τ</i>_s and <i>ω</i>_H, at low ionic concentrations, facilitating high mechanical performance of the ionogels due to viscoelastic energy dissipation. However, as the ionic concentration increased, a slight decoupling of <i>σ</i>_dc and <i>ω</i>_H was noted, leading to a substantial reduction in the mechanical properties of the ionogels. Ultimately, these ionogels demonstrate potential as polymer electrolytes for applications in flexible wearable devices.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Non-monotonic frictional behavior in the lubricated sliding of soft patterned surfaces.","authors":"Arash Kargar-Estahbanati, Bhargav Rallabandi","doi":"10.1039/d4sm01018c","DOIUrl":"https://doi.org/10.1039/d4sm01018c","url":null,"abstract":"<p><p>We study the lubricated contact of sliding soft surfaces that are locally patterned but globally cylindrical, held together under an external normal force. We consider gently engineered sinusoidal patterns with small slopes. Three dimensionless parameters govern the system: a speed, and the amplitude and wavelength of the pattern. Using numerical solutions of the Reynolds lubrication equation, we investigate the effects of these dimensionless parameters on key variables such as contact pressure and the coefficient of friction of the lubricated system. For small pattern amplitudes, the coefficient of friction increases with the amplitude. However, our findings reveal that increasing pattern amplitude beyond a critical value can decrease the friction coefficient, a result that contradicts conventional intuition and classical studies on the lubrication of rigid surfaces. For very large amplitudes, we show that the coefficient of friction drops even below the corresponding smooth case. We support these observations with a combination of perturbation theory and physical arguments, identifying scaling laws for large and small speeds, and for large and small pattern amplitudes. This study provides a quantitative understanding of friction in the contact of soft, wet objects and lays theoretical foundations for incorporating the friction coefficient into haptic feedback systems in soft robotics and haptic engineering.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Magnetic microwire rheometer reveals differences in hydrogel degradation <i>via</i> disulfide reducing agents.","authors":"Margaret Braunreuther, Justin Arenhoevel, Raju Bej, Cody Moose, Marcus A Mall, Rainer Haag, Gerald G Fuller","doi":"10.1039/d4sm01118j","DOIUrl":"https://doi.org/10.1039/d4sm01118j","url":null,"abstract":"<p><p>Mucus is composed of a complex network of mucin polymers connected by disulfide bonds. In muco-obstructive diseases, an increase in mucin disulfide crosslinks contributes to pathologic mucus formation, characterized by an increase in mucus viscosity and stiffness. Reducing agents that break down the disulfide bonds between mucins can be used to treat pathologic mucus and restore healthy mucus flow properties. Here, we compare three reducing agents <i>via</i> a rheological assay. A mucus-mimetic disulfide-crosslinked hyaluronic acid hydrogel was treated with thiolated dendritic polyglycerol sulfate (dPGS-SH), <i>N</i>-acetylcysteine (NAC), or dithiothreitol (DTT). A magnetic microwire rheometer was used to track the rheology of the hydrogel over time as the treatment degraded the sample. This nondestructive and minimally invasive technique reveals differences in the degradation mechanism between these reducing agents, with potential implications for drug delivery and the treatment of muco-obstructive diseases.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimizing the charge transport in redox-active gels: a computational study.","authors":"A V Sergeev, V Yu Rudyak, R A Samodelkin, E Yu Kozhunova, A V Chertovich","doi":"10.1039/d4sm01199f","DOIUrl":"https://doi.org/10.1039/d4sm01199f","url":null,"abstract":"<p><p>Redox-active polymer gels are promising materials for various applications, such as energy conversion and storage systems, organic electronics, soft-robotics, sensors and others. This is in part due to the remarkable structural tunability of these materials. The gel may adopt different conformations depending on the crosslinking density, solvent temperature and other conditions. These parameters affect its behavior, including the dynamics of the charge transport between the redox groups grafted to the polymer subchains, which is of utmost importance for electrochemical applications. Here, we employed coarse-grained molecular dynamics simulation to investigate the impact of crosslinking, redox group content and solvent quality on both subchain mobility and charge transport speed. In particular, unexpected behavior of the system under the theta-solvent condition was found and analyzed. The obtained results provide useful guidelines to facilitate the best conditions for enhanced \"redox induced\" conductivity in polymer gels, which would help the development of redox-flow batteries and other electrochemical devices.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamics of nanoparticle tracers in supercooled nanoparticle matrices.","authors":"Peter Edimeh, Ali H Slim, Jacinta C Conrad","doi":"10.1039/d4sm01106f","DOIUrl":"https://doi.org/10.1039/d4sm01106f","url":null,"abstract":"<p><p>We investigate the dynamics of tracer nanoparticles in bulk supercooled nanoparticle matrices using confocal microscopy. We mix fluorescent (tracer) and undyed (matrix) charged-stabilized polystyrene nanoparticles with tracer-to-matrix particle size ratios <i>δ</i> = 0.34, 0.36, 0.45, 0.71 at various matrix volume fractions <i>ϕ</i>. Single-particle and collective dynamics were obtained from particle-tracking algorithms and differential dynamic microscopy (DDM), respectively. The long-time behavior of the tracer mean-square displacement (MSD) and the shape of the distributions of particle displacements depend on <i>δ</i> and <i>ϕ</i>. At sufficiently large <i>ϕ</i>, small tracers (<i>δ</i> ≤ 0.36) remain mobile and subdiffusive but large tracers (<i>δ</i> ≥ 0.45) are dynamically arrested. The relaxation times determined from the intermediate scattering function (ISF) increase with <i>δ</i> and <i>ϕ</i>. Anomalous logarithmic decays in the ISF are observed for tracers of size <i>δ</i> ≤ 0.36 over a length scale of four to ten matrix particle diameters. These results provide insight into how penetrant size affects the transport of nanoparticles in porous media with soft interparticle interactions.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Strain hysteresis and Mullins effect of rubber vulcanizates with a reversible sacrificial network.","authors":"Rongyan Hu, Xin Jiang, Yaxin Chen, Jinlong Wang, Yuhao Guo, Qiang Zheng, Yonggang Shangguan","doi":"10.1039/d4sm01064g","DOIUrl":"https://doi.org/10.1039/d4sm01064g","url":null,"abstract":"<p><p>The incorporation of reversible sacrificial bonds is an important strategy for enhancing the mechanical properties of elastomers. However, the research on the viscoelasticity of vulcanized rubber with a reversible sacrificial bond network lags seriously. In this paper, the effects of metal coordination bonds on the mechanical properties of butadiene-styrene-vinylpyridine rubber vulcanizates (VPR) were systematically investigated. The experimental results showed that lower temperature and higher strain rate under smaller strain were advantageous in reflecting the significant contribution of sacrificial bonding. Compared with the conventional rubber nanocomposites, the sacrificial bond enhanced the energy dissipation while also improving reversible hysteresis energy and its proportion, revealing the origin of better self-healing and damping properties. The high-temperature rearrangement of sacrificial bonds promoted not only the recovery of mechanical properties, but also the recovery of covalent networks. The evolution mechanism of the network structure and viscoelasticity research under different thermal-mechanical coupling conditions could help to control the rubber network structure, providing a promising method for the regulation of the nonlinear behavior of rubber composites.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845436","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polyzwitterions: controlled synthesis, soft materials and applications.","authors":"Chenchen Gao, Yaning Gao, Qin Liu, Jinhua Tong, Hui Sun","doi":"10.1039/d4sm00674g","DOIUrl":"https://doi.org/10.1039/d4sm00674g","url":null,"abstract":"<p><p>Polyzwitterions refer to polymers containing both positive and negative charged groups in one side chain, which have shown unique physicochemical properties and significant potential in diverse applications due to their amphiphilic and net-neutral charged properties. This review aims to highlight the recent advances in the design and synthesis of polyzwitterions including direct polymerization of zwitterionic monomers and deionization of polymers. Furthermore, the formation of polyzwitterion based soft materials such as nanoparticles by self-assembly, hydrogels, coatings and polyzwitterion brushes, as well as the influence of the microstructure on their properties and applications are discussed. The potential applications of polyzwitterions in drug delivery, antifouling, lubrication, energy storage and antibacterial are also summarized. Finally, the prospects of polyzwitterions are proposed.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanocarriers for intracellular delivery of molecular payloads triggered by visible light.","authors":"Ashutosh Kanojiya, Julian Terglane, Volker Gerke, Bart Jan Ravoo","doi":"10.1039/d4sm01239a","DOIUrl":"https://doi.org/10.1039/d4sm01239a","url":null,"abstract":"<p><p>Stimuli-responsive nanocontainers have emerged as promising vehicles to deliver molecular payloads into the cytosol of cells in a spatially, temporally and dosage-controlled manner. These nanocontainers respond to a specific type of stimulus such as a change in redox status, enzymatic activity, pH, heat, light, and others. In this work, we introduce photoresponsive nanocontainers based on the self-assembly of vesicles with surface-confined cyclodextrin-adamantane host-guest chemistry. The nanocontainer surface is protected by a polymer shell with a tetrazine cross-linker that enables triggered delivery of payloads upon exposure to green light (515 nm). We show that the release of vesicle-encapsulated payload is achieved also in cells by visible light, which is less harmful than the UV-light responsive release reported previously for <i>in vitro</i> systems.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Soft hydrogel-embedded ceramic skeleton mimicking bone structure <i>via</i> sacrificial bond concept.","authors":"Sukamto, Miléna Lama, Jian Ping Gong, Takayuki Nonoyama","doi":"10.1039/d4sm01205d","DOIUrl":"https://doi.org/10.1039/d4sm01205d","url":null,"abstract":"<p><p>Bone, consisting of calcium phosphate minerals, rigid collagen fibrils, and acidic proteins, exhibits stiff and tough mechanical properties. On a molecular scale, covalent cross-linking in proteins and ionic interactions within proteins and at the protein-mineral boundary contribute to bone's toughness. In addition, hierarchical structures, like the sponge-like arrangement, are also crucial for the energy dissipation system in bone. Inspired by the multiple sacrificial bonds found in bone, we developed a soft/hard composite made up of two components with contrasting mechanical properties: a porous calcium phosphate skeleton and an acidic polymer hydrogel matrix. The porous ceramic skeleton alone is extremely rigid but brittle. However, the presence of the hydrogel matrix transforms the brittle nature of the porous ceramic skeleton into a soft/hard composite with stretchable and tough characteristics. The composite exhibits significant energy dissipation due to the fracture of the ceramic skeleton under small deformation, while catastrophic failure of the composite is prevented because the hybridized matrix disperses the damage throughout the entire sample. The Ca²⁺-mediated ionic bonding within the matrix hydrogel and at the boundary between the gel and skeleton effectively transfers the stress, enhancing the composite's toughness. Furthermore, the cyclic deformation generates new bare surfaces on the ceramic skeleton, leading to increased interaction between the matrix and these new surfaces, which enhances the composite's healing capability. This study demonstrates that the concept of multiple sacrificial bonds in bone is a smart strategy for designing polymer-ceramic composites with excellent mechanical properties.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}