Molecular Systems Design & Engineering最新文献

{"title":"Elucidating the interplay between entropy-driven and patch-mediated bonding in directing nanoscale assemblies†","authors":"Kireeti Akkunuri, Xiangyu Zhang and Thi Vo","doi":"10.1039/D4ME00153B","DOIUrl":"https://doi.org/10.1039/D4ME00153B","url":null,"abstract":"<p >Selective nanoparticle surface patterning presents incredible promise for broadening programmable materials design into a space beyond “close-packed” morphologies. These “patchy” particles impose directional attractions between neighbors that favor the formation of low-coordination, open structures previously inaccessible <em>via</em> their isotropically interacting nanoparticle counterparts. However, unlike patchy colloids, patches on nanoparticles are highly deformable, presenting challenges for their predictive design. Here, we present a multi-faceted approach combining theory and simulation to investigate the underlying forces governing interactions between nanoparticles with flexible patches. We first develop a thermodynamic perturbation theory to fundamentally capture the interplay between patch–patch merging and directional entropic forces in controlling particle organization. We then employ theoretical insights to explicitly consider how monomer geometry synergizes with monomer connectivity in sculpting the equilibrium morphologies for polymeric chains composed of anisotropic monomeric subunits. Theory predictions are then validated using simulations, with excellent agreement across both local and global length scales. Combined, our findings indicate that a large suite of orientational and structural diversity can be attained <em>via</em> precision engineering of how patch–patch and entropic forces between the anisotropic nanoparticles counterbalance each other. These findings on nanoscale patchy interactions offer newer avenues for directing the assembly process of novel polymeric and metamaterials.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 19-31"},"PeriodicalIF":3.2,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Wireframe DNA origami nanostructure with the controlled opening of edges","authors":"Maryam Mogheiseh and Reza Hasanzadeh Ghasemi","doi":"10.1039/D4ME00144C","DOIUrl":"https://doi.org/10.1039/D4ME00144C","url":null,"abstract":"<p >Wireframe DNA origami nanostructures present significant potential for a variety of applications in nanotechnology, primarily due to their straightforward design and construction processes. The precise control afforded by these nanostructures renders them exceptionally suitable for executing specific tasks. This study introduces innovative designs by altering short strands (staples) in wireframe DNA origami nanostructures, leading to different behaviors at human body temperature. These behaviors include the selective opening of certain parts of the structure while keeping other parts closed. Our research demonstrates that wireframe DNA origami nanostructures, with their numerous edges, can be engineered to allow selective opening of specific edges. This capability facilitates precise control over the structural configuration, enabling designers to customize these nanostructures to fulfill specific functional requirements. Consequently, the use of these controllable nanostructures opens up new avenues for developing nanorobots. By leveraging the unique properties of wireframe DNA origami, this study paves the way for advancements in the field of nanotechnology, particularly in the creation of versatile and adaptable nanoscale devices.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 68-80"},"PeriodicalIF":3.2,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced glucose-responsivity of PBA–diol hydrogel networks by reducing crosslink affinity†","authors":"Sijie Xian, Yuanhui Xiang, Svenja Deichmann and Matthew J. Webber","doi":"10.1039/D4ME00106K","DOIUrl":"https://doi.org/10.1039/D4ME00106K","url":null,"abstract":"<p >Glucose-responsive hydrogel systems are increasingly explored for insulin delivery, with dynamic-covalent crosslinking interactions between phenylboronic acids (PBA) and diols forming a key glucose-sensing mechanism. However, commonly used PBA and diol chemistries often have limited responsiveness to glucose under physiological concentrations. This is due, in part, to the binding of PBA to the commonly used diol chemistries having higher affinity than for PBA to glucose. The present study addresses this challenge by redesigning the diol chemistry in an effort to reduce its binding affinity to PBA, thereby enhancing the ability of glucose to compete with these redesigned PBA–diol crosslinks at its physiological concentration, thus improving responsiveness of the hydrogel network. Rheological analyses support enhanced sensitivity of these PBA–diol networks to glucose, while insulin release likewise improves from networks with reduced crosslink affinities. This work thus offers a new molecular design approach to improve glucose-responsive hydrogels for insulin delivery in diabetes management.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 40-49"},"PeriodicalIF":3.2,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d4me00106k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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":"Phenyl- versus cyclohexyl-terminated substituents: comparative study on aggregated structures and electron-transport properties in n-type organic semiconductors†","authors":"Shohei Kumagai, Takeru Koguma, Yutaro Arai, Go Watanabe, Hiroyuki Ishii, Jun Takeya and Toshihiro Okamoto","doi":"10.1039/D4ME00110A","DOIUrl":"https://doi.org/10.1039/D4ME00110A","url":null,"abstract":"<p >Substituent engineering is a key route to high-performance functional molecular materials in the same way as the development of a π-electron core for organic (opto-)electronics. Here we demonstrate a comparative study between aromatic phenyl- and aliphatic cyclohexyl-terminated side-chain substituents on an electron-deficient π-electron core, 3,4,9,10-benzo[<em>de</em>]isoquinolino[1,8-<em>gh</em>]quinolinetetracarboxylic diimide (BQQDI), to get insights into the impact of intermolecular interactions between the substituents in the solid state on high-performance electron-transport properties. In the BQQDI system, both phenyl- and cyclohexyl-terminated ethyl substituents show similar packing structures, demonstrating the unobvious impact of terminal groups. However, solution-processed single-crystal transistor studies revealed a relatively low electron mobility of cyclohexyl-terminated BQQDI. Based on molecular dynamics simulations, we attribute this discrepancy to dynamic molecular motions coupled with electronic coupling in the solid state. While phenyl groups in the phenylethyl substituent show intermolecular C–H⋯π interactions which lead to less dynamic motions, the cyclohexyl counterpart does not show any specific intermolecular interactions. Hence, a low-dynamic feature thanks to inter-side-chain interactions is promising for excellent charge-transport properties. The present findings underline the crucial role of interactions between substituents in the development of organic materials <em>via</em> side-chain-engineered control of the solid-state dynamic motions.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 32-39"},"PeriodicalIF":3.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual responsive fluorescence switching of organohydrogel towards base/acid†","authors":"Manish Kumar Dixit, Moupia Mukherjee, Bharat Kumar Sahu, Abul Kalam and Mrigendra Dubey","doi":"10.1039/D4ME00067F","DOIUrl":"https://doi.org/10.1039/D4ME00067F","url":null,"abstract":"<p >Herein, we have synthesized an ESIPT inbuilt novel tripodal gelator <strong>TH-AIL</strong>, which upon dissolution in DMSO followed by the addition of water (1 : 1) leads to the formation of a unique orange fluorescent organohydrogel (0.35% w/v, OHG). The obtained OHG reveals responses towards base NH<small>₃</small> and acid HCl by way of reversible change in fluorescence colour from orange to green along with restorable conversion from gel to sol phase.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1210-1214"},"PeriodicalIF":3.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The structural, electronic and thermodynamic properties of the designed p-benzoquinone based dicationic ionic liquids: insight from DFT–GD3 and QTAIM†","authors":"Hossein Roohi, Sajedeh Habibipour and Khatereh Ghauri","doi":"10.1039/D4ME00119B","DOIUrl":"https://doi.org/10.1039/D4ME00119B","url":null,"abstract":"&lt;p &gt;In this work, the impact of various anions on the physicochemical properties of the designed &lt;em&gt;p&lt;/em&gt;-benzoquinone-based dicationic ionic liquids &lt;strong&gt;[BTAD][A1–8]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; ([BTAD]&lt;small&gt;&lt;sup&gt;2+&lt;/sup&gt;&lt;/small&gt; = [&lt;em&gt;p&lt;/em&gt;-C&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;(N&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;2+&lt;/sup&gt;&lt;/small&gt; and A1–8 = [CH&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;CO&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [CF&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;CO&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [N(CN)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [CF&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;SO&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [ClO&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [BF&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;, [NTf&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt; and [PF&lt;small&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/small&gt;]&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt;) was investigated at the M06-2X/6-31++G(d,p) level of theory in the gas phase and solvent media. Besides, dispersion-corrected M06-2X-GD3, B2PLYP-GD3 and mPW2PLYP-GD2 functionals were employed to calculate the corrected interaction energies. The thermodynamic interaction energies in gas and solvent media, structural parameters, electrostatic potential maps, natural charge of atoms, charge transfer (CT), electron density properties, potentials of the anodic and cathodic limits (&lt;em&gt;V&lt;/em&gt;&lt;small&gt;&lt;sub&gt;AL&lt;/sub&gt;&lt;/small&gt; and &lt;em&gt;V&lt;/em&gt;&lt;small&gt;&lt;sub&gt;CL&lt;/sub&gt;&lt;/small&gt;), electrochemical windows (ECW), acidity (Δp&lt;em&gt;K&lt;/em&gt;&lt;small&gt;&lt;sub&gt;a1&lt;/sub&gt;&lt;/small&gt; and Δp&lt;em&gt;K&lt;/em&gt;&lt;small&gt;&lt;sub&gt;a2&lt;/sub&gt;&lt;/small&gt;) and reduced gradient density plots (RGD) were examined. Based on the corrected interaction energies, the stability order of &lt;strong&gt;[BTAD][A1–8]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; complexes at all levels of theory is &lt;strong&gt;[BTAD][CH&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;3&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;CO&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][CF&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;3&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;CO&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][N(CN)&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][CF&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;3&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;SO&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;3&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][ClO&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;4&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][BF&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;4&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt;&lt;strong&gt;]&lt;/strong&gt;&lt;small&gt;&lt;sub&gt;&lt;strong&gt;2&lt;/strong&gt;&lt;/sub&gt;&lt;/small&gt; &gt; &lt;strong&gt;[BTAD][NTf&lt;","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 1","pages":" 50-67"},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Promising vaccine models against astrovirus MLB2 using integrated vaccinomics and immunoinformatics approaches†","authors":"Syed Luqman Ali, Awais Ali, Waseef Ullah, Asifullah Khan, Elham Mohammed Khatrawi, Abdul Malik, Aigul Abduldayeva, Aliya Baiduissenova, Hind Jaber Althagafi and Deema Fallatah","doi":"10.1039/D3ME00192J","DOIUrl":"https://doi.org/10.1039/D3ME00192J","url":null,"abstract":"<p >Astrovirus MLB2 (AstV-MLB2) is an emerging gastrointestinal virus causing meningitis and disseminated infections. Currently, there are no vaccine-based therapies available for AstV-MLB2. This study aims to develop multi-epitope vaccine models using candidate proteins from AstV-MLB2. Highly immunogenic epitopes (IC<small>₅₀</small> &lt; 200 μM) exhibiting conservation, antigenicity, and non-allergenicity were called from these proteins. Additionally, the selection criteria for epitopes were based on their potential to trigger immune cells and stimulate IFN-γ-mediated immune responses. The model vaccine constructs were designed from identified lead epitopes, along with immune-enhancer adjuvants and linker sequences. The proposed vaccine models were assessed for allergenicity, antigenicity, and structural integrity to ensure their safety and effectiveness. The binding potential of the vaccine models to HLA and TLR-4 immune cell receptors was evaluated to identify their capacity to stimulate immune responses. Among several raw constructs, MLB2-V1 and MLB2-V2 were identified as potential vaccine candidates due to their non-allergenic features, enhanced antigenic properties, and structural stability. Both these constructs were extensively evaluated and predicted to effectively bind to and interact with immune cell receptors, potentially triggering cellular and innate immune responses. Additionally, the prioritized constructs were deemed suitable for cloning and expression using recombinant DNA systems. The model vaccine constructs showed promise, warranting further investigation into their immune efficacy against MLB2-mediated infections through experimental assays and clinical trials.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1285-1299"},"PeriodicalIF":3.2,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graph-based networks for accurate prediction of ground and excited state molecular properties from minimal features†","authors":"Denish Trivedi, Kalyani Patrikar and Anirban Mondal","doi":"10.1039/D4ME00113C","DOIUrl":"https://doi.org/10.1039/D4ME00113C","url":null,"abstract":"<p >Graph neural networks (GNN) have been demonstrated to correlate molecular structure with properties, enabling rapid evaluation of molecules for a given application. Molecular properties, including ground and excited states, are crucial to analyzing molecular behavior. However, while attention-based mechanisms and pooling methods have been optimized to accurately predict specific properties, no versatile models can predict diverse molecular properties. Here, we present graph neural networks that predict a wide range of properties with high accuracy. Model performance is high regardless of dataset size and origin. Further, we demonstrate an implementation of hierarchical pooling enabling high-accuracy prediction of excited state properties by effectively weighing aspects of features that correlate better with target properties. We show that graph attention networks consistently outperform convolution networks and linear regression, particularly for small dataset sizes. The graph attention model is more accurate than previous message-passing neural networks developed for the prediction of diverse molecular properties. Hence, the model is an efficient tool for screening and designing molecules for applications that require tuning multiple molecular properties.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1275-1284"},"PeriodicalIF":3.2,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-consistent field theory and coarse-grained molecular dynamics simulations of pentablock copolymer melt phase behavior†","authors":"So Jung Park, Tristan Myers, Vinson Liao and Arthi Jayaraman","doi":"10.1039/D4ME00138A","DOIUrl":"https://doi.org/10.1039/D4ME00138A","url":null,"abstract":"<p >Block copolymer (BCP) self-assembly leads to nanostructured materials with diverse ordered morphologies, some of which are attractive for transport applications. Multiblock AB copolymers are of interest as they offer a larger design parameter space than diblock copolymers allowing researchers to tailor their self-assembly to achieve target morphologies. In this study, we investigate the phase behavior of symmetric A<small>_<em>x</em></small>B<small>_<em>y</em></small>A<small>_<em>z</em></small>B<small>_<em>y</em></small>A<small>_<em>x</em></small> and B<small>_<em>x</em></small>A<small>_<em>y</em></small>B<small>_<em>z</em></small>A<small>_<em>y</em></small>B<small>_<em>x</em></small> pentablock copolymers (pentaBCPs) where A and B monomers have the same statistical segment length. We use a combination of self-consistent field theory (SCFT) calculations and molecular dynamics (MD) simulations to link the polymer design parameters, namely the fraction of middle block volume to the volume of all blocks of same type, <em>τ</em>, overall volume fraction of A block, <em>f</em><small>_A</small>, and segregation strength, <em>χN</em>, to the equilibrium morphologies and the distributions of chain conformations in these morphologies. In the phase diagrams calculated using SCFT, we observe broader double gyroid windows and the existence of lamellar morphologies even at small values <em>f</em><small>_A</small> in contrast to what has been seen for diblock copolymers. We also see a reentrant phase sequence of double gyroid → cylinder → lamellae → cylinder → double gyroid with increasing <em>τ</em> at fixed <em>f</em><small>_A</small>. The chain conformations adopted in these morphologies are sampled in coarse-grained MD simulations and quantified with distributions of the chain end-to-end distance and fractions of chains whose middle (A or B) and end (A or B) blocks remain within domains of same chemistry (A or B). These analyses show that the pentaBCP chains adopt “looping”, “bridging”, and “hybrid” (both looping and bridging) conformations, with a majority of the chains adopting the hybrid conformation. The spatial distributions for each of the blocks in the pentaBCPs show that blocks of the same type in a chain locally segregate within the same domains, with shorter blocks segregating towards the domain boundaries and longer blocks filling the domain interior. This combined SCFT-MD approach enables us to rapidly screen the extensive pentaBCP design space to identify design rules for transport-favorable morphologies as well as verify the chain conformations and spatial arrangements associated with the theory predicted reentrant phase behavior.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1235-1253"},"PeriodicalIF":3.2,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/me/d4me00138a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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":"Molecular design of protein-based materials – state of the art, opportunities and challenges at the interface between materials engineering and synthetic biology","authors":"Ebony Shire, André A. B. Coimbra, Carlos Barba Ostria, Leonardo Rios-Solis and Diego López Barreiro","doi":"10.1039/D4ME00122B","DOIUrl":"10.1039/D4ME00122B","url":null,"abstract":"<p >Structural proteins like silk, squid ring teeth, elastin, collagen, or resilin, among others, are inspiring the development of new sustainable biopolymeric materials for applications including healthcare, food, soft robotics, or textiles. Furthermore, advances in the fields of soft materials and synthetic biology have a joint great potential to guide the design of novel structural proteins, despite both fields progressing mostly in a separate fashion so far. Using recombinant DNA technologies and microbial fermentations, we can design new structural proteins with monomer-level sequence control and a dispersity of <em>ca.</em> 1.0, based on permutations of tandem repeats derived from natural structural proteins. However, the molecular design of recombinant and repetitive structural proteins is a nontrivial task that is generally approached using low-throughput trial-and-error experimentation. Here, we review recent progress in this area, in terms of structure–function relationships and DNA synthesis technologies. We also discuss experimental and computational advances towards the establishment of rapid prototyping pipelines for this family of biopolymers. Finally, we highlight future challenges to make protein-based materials a commercially viable alternative to current fossil-based polymers.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 12","pages":" 1187-1209"},"PeriodicalIF":3.2,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/me/d4me00122b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142269140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}