Macromolecular Theory and Simulations最新文献

{"title":"Application of Conformation-Dependent Cyclization Model to Free-Radical Crosslinking Copolymerization With Polymeric Divinyl Monomers: Kinetics, Gel Point, Mesh Size and Network Dimensions","authors":"Hidetaka Tobita","doi":"10.1002/mats.70062","DOIUrl":"https://doi.org/10.1002/mats.70062","url":null,"abstract":"<div>\u0000 \u0000 <p>A recently proposed model that accounts for conformation-dependent intramolecular crosslinking is extended and applied to investigate free-radical crosslinking copolymerization where monodisperse polymeric crosslinkers are used. Uniform miniemulsion droplets, each consisting of <i>N</i>_M0 = 2 × 10⁵ monomer molecules including a polymeric divinyl monomer, are used for the Monte Carlo simulation. It is shown that the use of a polymeric crosslinker effectively suppresses the primary cyclization that is formed within a single primary chain, and the gel point approaches that predicted by the classical gelation theory. The mesh size of the resulting polymer network is significantly increased compared to that of the low molecular weight crosslinkers. The spatial size of an inhomogeneous network polymer is generally larger than that of a homogeneous random network, since regions of low crosslinking density dominate the size. The use of monodisperse polymeric crosslinkers imparts regularity and reduces the three-dimensional (3D) size, whereas the conformation-dependent intramolecular reactions introduce heterogeneity, which contributes to dimensional expansion. The 3D size is determined by the balance between these two opposing effects. The conformation-dependent cyclization model allows for a detailed analysis of how polymeric crosslinkers alter the network structure and its properties.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 6","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149146981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D Cellular Automata of Polymer Structural Response to Solvent Quality","authors":"Vasilii Korotenko,&nbsp;Irina Smirnova,&nbsp;Pavel Gurikov","doi":"10.1002/mats.70060","DOIUrl":"https://doi.org/10.1002/mats.70060","url":null,"abstract":"<p>A three-dimensional cellular automaton (3DCA) model is presented for describing the structural response of polymer systems to solvent quality. Polymer segments occupy a cubic lattice and evolve through local solvent-polymer exchange moves with fixed chain connectivity, excluded volume, bond-crossing rejection, nearest-neighbor interactions, and Metropolis-type acceptance. Solvent quality is controlled by the solvent-polymer interaction energy, while polymer-polymer cohesion is described by a separate contact energy. The model reproduces distinct poor-, θ-, and good-solvent regimes, including chain collapse, intermediate coil conformations, swelling, and aggregation. Radius-of-gyration scaling identifies the θ condition through a Flory exponent close to 0.50 and provides a basis for relating the lattice interaction energies to the Flory-Huggins parameter. Multichain simulations further show that chain topology strongly affects structural evolution: finite chains undergo pronounced restructuring associated with free chain ends, whereas periodically self-connected chains preserve fibrillar and system-spanning morphologies more effectively. The model therefore provides a minimal and transparent framework for linking local interaction rules to solvent-dependent mesoscale polymer structure, supported by an openly available simulation-to-figure workflow.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 6","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.70060","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149011599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Issue Information: Macromol. Theory Simul. 6/2026","authors":"","doi":"10.1002/mats.70061","DOIUrl":"https://doi.org/10.1002/mats.70061","url":null,"abstract":"","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 6","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.70061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149011598","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coarse-Grained Simulation Study on Gradient-Free Radical Polymerization via a Beer's Law-Based Heterogeneous Initiation Model","authors":"Bingbing Pan,&nbsp;Yiyi Zhang,&nbsp;Wen Li,&nbsp;Zhenbin Chen,&nbsp;Hong Liu,&nbsp;Hui Li","doi":"10.1002/mats.70059","DOIUrl":"https://doi.org/10.1002/mats.70059","url":null,"abstract":"<div>\u0000 \u0000 <p>Gradient polymer materials exhibit great potential for applications in fields such as sensors and biomedicine. While photoinitiated radical polymerization represents a common strategy for gradient fabrication, mesoscopic insights into polymerization kinetics and topological evolution under the control of gradient initiation—similar to photoinitiation—remain limited. In this study, using CGMD simulations, we developed a radical polymerization model incorporating a space-dependent initiation rate inspired by the mathematical form of Beer's Law. This model was utilized to investigate the reaction kinetics, topological features, and mechanical responses of radical polymerization under a decaying initiation reaction. The results indicate that the decay of the initiation reaction induces spatio-temporal discrepancies in the reactions within the system. In highly graded systems, small clusters preferentially form and merge in the high-initiation region, whereas the low-initiation region exhibits a pronounced reaction lag due to kinetic inhibition, ultimately yielding a gradient distribution of particles and crosslinkers. Under this kinetic heterogeneity, the fraction of “bridges” (elastically effective chains) decreases in the top region but increases in the bottom region due to prolonged free-radical lifetimes, thereby optimizing the overall topological structure. Mechanical analysis confirms that the initiation decay marginally enhances the overall mechanical performance while reallocating the stress-bearing capacity toward the high-initiation region.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148943304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Viscoelastic Response of Crosslinked Rubber: Coarse-Grained Molecular Dynamics and Time-Temperature Superposition","authors":"Kazuki Hisai,&nbsp;Yoshiaki Kawagoe,&nbsp;Tomonaga Okabe","doi":"10.1002/mats.70058","DOIUrl":"https://doi.org/10.1002/mats.70058","url":null,"abstract":"<p>The viscoelastic response of crosslinked rubber was investigated using coarse-grained molecular dynamics simulations combined with time-temperature superposition. Crosslinked polymer networks containing different numbers of crosslinkers were generated using a dynamic reaction probability model and their mechanical responses were analyzed by Green-Kubo-based stress autocorrelation and uniaxial tensile simulations. The relaxation master curves were constructed from the relaxation modulus and loss tangent, extending the accessible timescale by nearly seven orders of magnitude beyond that directly attainable in the simulation. Increasing the number of crosslinkers slowed the stress relaxation, reduced the peak value of the loss tangent, and increased the equilibrium modulus, indicating that crosslinking suppressed the viscous relaxation and enhanced the elastic network constraints. Stress decomposition further revealed that intermediate-time relaxation is strongly affected by negative cross-correlations between the pair and bonded stresses, whereas the long-time equilibrium elasticity in highly crosslinked systems is sustained mainly by the autocorrelation and cross-correlation of the backbone-bond and crosslink-bond stresses. In addition, uniaxial tensile simulations showed that crosslinking promotes chain orientation and that crosslink bonds undergo greater stretching than backbone bonds near the onset of strain hardening. These results provide a molecular-scale picture of how crosslinking governs both the stress relaxation and elastic reinforcement of rubber.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.70058","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydration-Interaction Balance Controls Morphological Landscapes in Peptide-Polymer Amphiphiles","authors":"Sabila K. Pinky,&nbsp;Nicholas Calzadilla,&nbsp;Benjamin P. Allen,&nbsp;Abigail S. Knight,&nbsp;Yaroslava G. Yingling","doi":"10.1002/mats.70057","DOIUrl":"https://doi.org/10.1002/mats.70057","url":null,"abstract":"<p>Peptide-polymer amphiphiles (PPAs) form diverse nanostructures with tunable properties, yet predicting and tuning these morphologies remains challenging due to complex molecular interactions. We systematically investigated the self-assembly of PPAs with a random coil peptide (XTEN2) base and varying side chains of an oligo (alkyl acrylate) tail (ethyl, <i>n</i>-butyl, <i>tert</i>-butyl, hexyl, and cyclohexyl) using large-scale all-atom molecular dynamics (AMD) simulations validated by experimental observations. Our results revealed that the formation of various micellar morphologies, such as worm-like, perforated, spherical, and multi-core assemblies, is governed by the balance between tail-to-tail and tail-to-water interaction energies, in addition to core hydration levels. Spherical and multi-core morphologies form when tail-to-tail interactions dominate, whereas worm-like and perforated structures form as tail-to-water interactions increase. Additionally, peptide secondary structure dictated by sequence plays an important role in driving assembly, with β-sheet-rich conformations promoting more compact cores. These findings elucidate how subtle tail architecture variations direct PPA self-assembly, providing molecular-level insights that align with experimental particle sizes. This work advances the rational design of PPA-based nanomaterials by linking molecular interactions to morphology control.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.70057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetic Analysis of Polymer Crystallization Using the Hoffman–Lauritzen Model","authors":"Alireza Aghili,&nbsp;Amir Hossein Haghighi,&nbsp;Seyed Mohammad Hajji Khorasani","doi":"10.1002/mats.70056","DOIUrl":"https://doi.org/10.1002/mats.70056","url":null,"abstract":"<div>\u0000 \u0000 <p>This study presents a new method for analyzing the kinetics of glass and melt crystallization of polymers using the Hoffman–Lauritzen model. The method includes two steps: first, the crystallization rate is decomposed into a conversion function and a rate constant, applicable to both isothermal and nonisothermal data. Second, the extracted rate constant is used to determine the Hoffman–Lauritzen parameters, with the method performing best for nonisothermal conditions. The accuracy of the new approach was verified through simulated crystallization processes and demonstrated experimentally using glass and melt crystallization of poly(ethylene 2,5-furandicarboxylate). A major advantage of the newly proposed approach is its exclusive reliance on multiple linear regression, which guarantees unique global least-squares solutions without the need for initial guesses or iterative trial-and-error methods. GNU Octave/MATLAB scripts are supplied to facilitate practical implementation of the newly proposed method.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753355","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Properties of Ideal Two-Dimensional Snowflake Polymers","authors":"Matthew Jura,&nbsp;Marvin Bishop","doi":"10.1002/mats.70053","DOIUrl":"https://doi.org/10.1002/mats.70053","url":null,"abstract":"<div>\u0000 \u0000 <p>The properties of ideal two-dimensional snowflake polymers containing 601 to 1342 units are investigated with a Monte Carlo growth method. The mean-square radius of gyration, the <span></span><math>\u0000 <semantics>\u0000 <mi>g</mi>\u0000 <annotation>$g$</annotation>\u0000 </semantics></math>-ratio, the asphericity, and the scattering function are calculated. A graph theory approach is employed to obtain exact scattering functions using a technique for counting paths in the graph representation of the polymers. The simulation results are in very good agreement with theoretical predictions, and with previous studies in three dimensions, by K. Haydukivska, V. Blavatska, J. Pature, J. Mole. Liq., 2023, <b>392</b>, 123430.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148696254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"PolymInsight: An Open Process Simulation Software for Polymerization With Microstructural Quality Indices","authors":"Xiaowen Lin,&nbsp;Rui Liu,&nbsp;Muqian Zhang,&nbsp;Shenhua Jiao,&nbsp;Xi Chen","doi":"10.1002/mats.70051","DOIUrl":"https://doi.org/10.1002/mats.70051","url":null,"abstract":"<div>\u0000 \u0000 <p>Modeling and optimization of polymerization processes incorporating microstructural quality indices are crucial for determining optimal design and operational strategies in polymer production. However, existing polymerization models that account for these indices are often characterized by large-scale, nonlinear, and coupled equations, presenting significant computational challenges. Moreover, limited research has been conducted on developing algorithms for accurately predicting polymer microscopic properties, and only a few software tools are capable of simulating and optimizing such complex processes. To address these challenges, this study introduces “<i>PolymInsight</i>,” an innovative software tool developed in an open-source Python environment, designed specifically for modeling polymerization processes with microstructural quality indices. <i>PolymInsight</i> supports both dynamic modeling of batch reactors and steady-state modeling of continuous stirred tank reactors across a variety of polymerization reactions. The software's logical architecture includes a graphical user interface, a robust data structure, a general modeling framework, model reduction techniques, and an adaptive solution strategy. Case studies demonstrate the effectiveness, accuracy, and generalizability of <i>PolymInsight</i>, highlighting its potential as a powerful tool for research and industrial applications in polymer science.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148696252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Miscibility in Polyethylene Blends Influenced by Weight Fractions and Short-Chain Branching: A Molecular Dynamics Study","authors":"Farhan Ahmad Pasha,&nbsp;Francisco Perez Valencia,&nbsp;Antonios Doufas","doi":"10.1002/mats.70052","DOIUrl":"https://doi.org/10.1002/mats.70052","url":null,"abstract":"<div>\u0000 \u0000 <p>Polyethylene (PE), a versatile polymer, exhibits varying degrees of miscibility depending on molecular weight distribution, relative component concentrations (split ratio), and short-chain branching (SCB) content. This study investigates the thermodynamic factors governing miscibility in bimodal PE blends composed of low-molecular-weight polyethylene (LMwPE) and high-molecular-weight polyethylene (HMwPE), with emphasis on the effects of SCB and split ratio. Molecular dynamics (MD)-based solubility parameters, mixing energy (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>Δ</mi>\u0000 <msub>\u0000 <mi>E</mi>\u0000 <mrow>\u0000 <mi>m</mi>\u0000 <mi>i</mi>\u0000 <mi>x</mi>\u0000 </mrow>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>${{Delta}}{{E}_{mix}}$</annotation>\u0000 </semantics></math>), and the Flory-Huggins interaction parameter (<span></span><math>\u0000 <semantics>\u0000 <mi>χ</mi>\u0000 <annotation>$chi $</annotation>\u0000 </semantics></math>)were used to determine miscibility thresholds in PE systems. Molecular weight influences chain interaction energies, free volume, and cohesive energy density, thereby affecting blend compatibility. In the absence of SCB, equal-weight blends exhibit higher miscibility than disproportionate blends, demonstrating the importance of the split ratio. SCB content further affects miscibility depending on its concentration in the blend components and the split ratio. In disproportionate blends where SCB-containing components are minor, increased SCB enhances miscibility, whereas in equal-weight blends, SCB reduces compatibility. SCB disrupts chain packing and promotes chain interpenetration by increasing free volume, improving compatibility at specific blend ratios. Overall, SCB influences packing efficiency, interaction energies, and phase-separation behavior, providing molecular-level insights for designing bimodal high-density polyethylene systems with controlled phase behavior.</p>\u0000 </div>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"35 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148696253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}