ACS Materials Au最新文献

{"title":"Bacterial-Nanocellulose-Based Biointerfaces and Biomimetic Constructs for Blood-Contacting Medical Applications","authors":"Erin L. Roberts,&nbsp;Sorosh Abdollahi,&nbsp;Fereshteh Oustadi,&nbsp;Emma D. Stephens and Maryam Badv*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00021","DOIUrl":"10.1021/acsmaterialsau.3c00021","url":null,"abstract":"<p >Understanding the interaction between biomaterials and blood is critical in the design of novel biomaterials for use in biomedical applications. Depending on the application, biomaterials can be designed to promote hemostasis, slow or stop bleeding in an internal or external wound, or prevent thrombosis for use in permanent or temporary medical implants. Bacterial nanocellulose (BNC) is a natural, biocompatible biopolymer that has recently gained interest for its potential use in blood-contacting biomedical applications (e.g., artificial vascular grafts), due to its high porosity, shapeability, and tissue-like properties. To promote hemostasis, BNC has been modified through oxidation or functionalization with various peptides, proteins, polysaccharides, and minerals that interact with the coagulation cascade. For use as an artificial vascular graft or to promote vascularization, BNC has been extensively researched, with studies investigating different modification techniques to enhance endothelialization such as functionalizing with adhesion peptides or extracellular matrix (ECM) proteins as well as tuning the structural properties of BNC such as surface roughness, pore size, and fiber size. While BNC inherently exhibits comparable mechanical characteristics to endogenous blood vessels, these mechanical properties can be enhanced through chemical functionalization or through altering the fabrication method. In this review, we provide a comprehensive overview of the various modification techniques that have been implemented to enhance the suitability of BNC for blood-contacting biomedical applications and different testing techniques that can be applied to evaluate their performance. Initially, we focused on the modification techniques that have been applied to BNC for hemostatic applications. Subsequently, we outline the different methods used for the production of BNC-based artificial vascular grafts and to generate vasculature in tissue engineered constructs. This sequential organization enables a clear and concise discussion of the various modifications of BNC for different blood-contacting biomedical applications and highlights the diverse and versatile nature of BNC as a natural biomaterial.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"418–441"},"PeriodicalIF":0.0,"publicationDate":"2023-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47347655","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":"Resorbable Membranes for Guided Bone Regeneration: Critical Features, Potentials, and Limitations","authors":"Sara Abtahi,&nbsp;Xiaohu Chen,&nbsp;Sima Shahabi and Noushin Nasiri*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00013","DOIUrl":"10.1021/acsmaterialsau.3c00013","url":null,"abstract":"<p >Lack of horizontal and vertical bone at the site of an implant can lead to significant clinical problems that need to be addressed before implant treatment can take place. Guided bone regeneration (GBR) is a commonly used surgical procedure that employs a barrier membrane to encourage the growth of new bone tissue in areas where bone has been lost due to injury or disease. It is a promising approach to achieve desired repair in bone tissue and is widely accepted and used in approximately 40% of patients with bone defects. In this Review, we provide a comprehensive examination of recent advances in resorbable membranes for GBR including natural materials such as chitosan, collagen, silk fibroin, along with synthetic materials such as polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene glycol (PEG), and their copolymers. In addition, the properties of these materials including foreign body reaction, mechanical stability, antibacterial property, and growth factor delivery performance will be compared and discussed. Finally, future directions for resorbable membrane development and potential clinical applications will be highlighted.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"394–417"},"PeriodicalIF":0.0,"publicationDate":"2023-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41847826","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":"Thermally Induced Oxygen Vacancies and High Oxide Ion Conduction in K2ZnV2O7 with a Melilite-Related Structure","authors":"Huina Wei,&nbsp;Jiazheng Hao,&nbsp;Jian Yang,&nbsp;Yun Lv,&nbsp;Feiran Shen,&nbsp;Wenda Zhang,&nbsp;Jie Chen,&nbsp;Lunhua He*,&nbsp;Laijun Liu,&nbsp;Xiaojun Kuang and Jungu Xu*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00022","DOIUrl":"10.1021/acsmaterialsau.3c00022","url":null,"abstract":"<p >Donor-doped melilite materials with interstitial oxygen defects in the structure are good oxide ion conductors with negligible electronic conduction and show great potential in the ceramic electrolyte of intermediate-temperature solid oxide fuel cells (IT-SOFC). However, the parent melilite-structured materials with stoichiometric oxygen are usually insulators. Herein, we reported high and pure oxide ion conduction in the parent K₂ZnV₂O₇ material with a melilite-related structure, e.g., ∼1.14 × 10^–3 S/cm at 600 °C, which is comparable to that of the state-of-the-art yttrial-stabilized ZrO₂ applied in practical fuel cells. Neutron diffraction data revealed the interesting thermally induced formation of oxygen vacancies at elevated temperatures, which triggered the transformation of the material from electronically conducting to purely and highly oxide ion-conducting. The VO₄ tetrahedron with non-bridging terminal oxygen in K₂ZnV₂O₇ was proved to be the key structural factor for transporting oxygen vacancies. The molecular dynamic simulation based on the interatomic potential approach revealed that long-range oxide ion diffusion was achieved by breaking and re-forming the 5-fold MO₄ (M = Zn and V) tetrahedral rings. These findings enriched our knowledge of melilite and melilite-related materials, and creating oxygen vacancies in a melilite-related material may be a new strategy for developing novel oxide ion conductors.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"492–500"},"PeriodicalIF":0.0,"publicationDate":"2023-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45545970","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":"Investigation of Gold Nanoparticle Naproxen-Derived Conjugations in Ovarian Cancer","authors":"Cansu Umran Tunc,&nbsp;Gizem Kursunluoglu,&nbsp;Munevver Akdeniz,&nbsp;Aybuke Ulku Kutlu,&nbsp;Muhammed Ihsan Han,&nbsp;Mukerrem Betul Yerer and Omer Aydin*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00033","DOIUrl":"10.1021/acsmaterialsau.3c00033","url":null,"abstract":"<p >Ovarian cancer, which is one of the most diagnosed cancer types among women, maintains its significance as a global health problem. Several drug candidates have been investigated for the potential treatment of ovarian cancer. Nonsteroidal anti-inflammatory drugs (NSAIDs) demonstrated anti-cancer activity through the inhibition of cyclooxygenase 2 (COX-2) and by inhibiting COX-2-dependent prostaglandin (PG) production. Naproxen is one of the most used NSAIDs and Naproxen-derived compounds (NDCs) may show potential treatment effects on cancer as chemotherapeutic drugs. Although there are successful drug development studies, the lack of solubility of these drug candidates in aqueous media results in limited bioavailability and high variability of patient responses during treatment. Low aqueous solubility is one of the main problems in the pharmaceutical industry in terms of drug development. Nanotechnology-based strategies provide solutions to hydrophobic drug limitations by increasing dispersion and improving internalization. In this study, two different NDCs (NDC-1 and NDC-2) bearing a thiosemicarbazide/1,2,4-triazole moiety were synthesized and tested for chemotherapeutic effects on ovarian cancer cells, which have a high COX-2 expression. To overcome the limited dispersion of these hydrophobic drugs, the drug molecules were conjugated to the surface of 13 nm AuNPs. Conjugation of drugs to AuNPs increased the distribution of drugs in aqueous media, and NDC@AuNP conjugates exhibited excellent colloidal stability for up to 8 weeks. The proposed system demonstrated an increased chemotherapeutic effect than the free drug counterparts with at least 5 times lower IC50 values. NDC@AuNP nanosystems induced higher apoptosis rates, which established a simple and novel way to investigate activity of prospective drugs in drug discovery research.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"483–491"},"PeriodicalIF":0.0,"publicationDate":"2023-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44841955","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":"Electrospun Poly(vinyl alcohol)-Based Conductive Semi-interpenetrating Polymer Network Fibrous Hydrogel: A Toolbox for Optimal Cross-Linking","authors":"Anna Zakrzewska,&nbsp;Seyed Shahrooz Zargarian,&nbsp;Chiara Rinoldi,&nbsp;Arkadiusz Gradys,&nbsp;Dariusz Jarząbek,&nbsp;Michele Zanoni,&nbsp;Chiara Gualandi,&nbsp;Massimiliano Lanzi and Filippo Pierini*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00025","DOIUrl":"10.1021/acsmaterialsau.3c00025","url":null,"abstract":"<p >Cross-linking of poly(vinyl alcohol) (PVA) creates a three-dimensional network by bonding adjacent polymer chains. The cross-linked structure, upon immersion in water, turns into a hydrogel, which exhibits unique absorption properties due to the presence of hydrophilic groups within the PVA polymer chains and, simultaneously, ceases to be soluble in water. The properties of PVA can be adjusted by chemical modification or blending with other substances, such as polymers, <i>e.g</i>., conductive poly[3-(potassium-5-butanoate)thiophene-2,5-diyl] (P3KBT). In this work, PVA-based conductive semi-interpenetrating polymer networks (semi-IPNs) are successfully fabricated. The systems are obtained as a result of electrospinning of PVA/P3KBT precursor solutions with different polymer concentrations and then cross-linking using “green”, environmentally safe methods. One approach consists of thermal treatment (H), while the second approach combines stabilization with ethanol and heating (E). The comprehensive characterization allows to evaluate the correlation between the cross-linking methods and properties of nanofibrous hydrogels. While both methods are successful, the cross-linking density is higher in the thermally cross-linked samples, resulting in lower conductivity and swelling ratio compared to the E-treated samples. Moreover, the H-cross-linked systems have better mechanical properties─lower stiffness and greater tensile strength. All the tested systems are biocompatible, and interestingly, due to the presence of P3KBT, they show photoresponsivity to solar radiation generated by the simulator. The results indicate that both methods of PVA cross-linking are highly effective and can be applied to a specific system depending on the target, <i>e.g</i>., biomedical or electronic applications.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"464–482"},"PeriodicalIF":0.0,"publicationDate":"2023-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42519699","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":"Highly Active and Durable Rh–Mo-Based Catalyst for the NO–CO–C3H6–O2 Reaction Prepared by Using Hybrid Clustering","authors":"Shun Hayashi*,&nbsp;Shinji Endo,&nbsp;Hiroki Miura and Tetsuya Shishido*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00001","DOIUrl":"10.1021/acsmaterialsau.3c00001","url":null,"abstract":"<p >We developed a method for preparing catalysts by using hybrid clustering to form a high density of metal/oxide interfacial active sites. A Rh–Mo hybrid clustering catalyst was prepared by using a hybrid cluster, [(RhCp*)₄Mo₄O₁₆] (Cp* = η⁵-C₅Me₅), as the precursor. The activities of the Rh–Mo catalysts toward the NO–CO–C₃H₆–O₂ reaction depended on the mixing method (hybrid clustering &gt; coimpregnation ≈ pristine Rh). The hybrid clustering catalyst also exhibited high durability against thermal aging at 1273 K in air. The activity and durability were attributed to the formation of a high-density of Rh/MoO_<i>x</i> interfacial sites. The NO reduction mechanism on the hybrid clustering catalyst was different from that on typical Rh catalysts, where the key step is the N–O cleavage of adsorbed NO. The reducibility of the Rh/MoO_<i>x</i> interfacial sites contributed to the partial oxidation of C₃H₆ to form acetate species, which reacted with NO+O₂ to form N₂ via the adsorbed NCO species. The formation of reduced Rh on Rh₄Mo₄/Al₂O₃ was not as essential as that on typical Rh catalysts; this explained the improvement in durability.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"456–463"},"PeriodicalIF":0.0,"publicationDate":"2023-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42152464","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":"Anisotropic Phonon Bands in H-Bonded Molecular Crystals: The Instructive Case of α-Quinacridone","authors":"Lukas Legenstein,&nbsp;Lukas Reicht,&nbsp;Tomas Kamencek and Egbert Zojer*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00011","DOIUrl":"10.1021/acsmaterialsau.3c00011","url":null,"abstract":"<p >Phonons play a crucial role in the thermodynamic and transport properties of solid materials. Nevertheless, rather little is known about phonons in organic semiconductors. Thus, we employ highly reliable quantum mechanical calculations for studying the phonons in the α-polymorph of quinacridone. This material is particularly interesting, as it has highly anisotropic properties with distinctly different bonding types (H-bonding, π-stacking, and dispersion interactions) in different spatial directions. By calculating the overlaps of modes in molecular quinacridone and the α-polymorph, we associate Γ-point phonons with molecular vibrations to get a first impression of the impact of the crystalline environment. The situation becomes considerably more complex when analyzing phonons in the entire 1st Brillouin zone, where, due to the low symmetry of α-quinacridone, a multitude of avoided band crossings occur. At these, the character of the phonon modes typically switches, as can be inferred from mode participation ratios and mode longitudinalities. Notably, avoided crossings are observed not only as a function of the length but also as a function of the direction of the phonon wave vector. Analyzing these avoided crossings reveals how it is possible that the highest frequency acoustic band is always the one with the largest longitudinality, although longitudinal phonons in different crystalline directions are characterized by fundamentally different molecular displacements. The multiple avoided crossings also give rise to a particularly complex angular dependence of the group velocities, but combining the insights from the various studied quantities still allows drawing general conclusions, e.g., on the relative energetics of longitudinal vs transverse deformations (i.e., compressions and expansions vs slips of neighboring molecules). They also reveal how phonon transport in α-quinacridone is impacted by the reinforcing H-bonds and by π-stacking interactions (resulting from a complex superposition of van der Waals, charge penetration, and exchange repulsion).</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 4","pages":"371–385"},"PeriodicalIF":0.0,"publicationDate":"2023-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00011","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48016980","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":"Light-Controlled Cell–Cell Assembly Using Photocaged Oligonucleotides","authors":"Katelyn Mathis,&nbsp;Afia Ibnat Kohon,&nbsp;Stephen Black and Brian Meckes*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00020","DOIUrl":"10.1021/acsmaterialsau.3c00020","url":null,"abstract":"<p >The interactions between heterogeneous cell populations play important roles in dictating various cell behaviors. Cell–cell contact mediates communication through the exchange of signaling molecules, electrical coupling, and direct membrane-linked ligand–receptor interactions. In vitro culturing of multiple cell types with control over their specific arrangement is difficult, especially in three-dimensional (3D) systems. While techniques that allow one to control the arrangement of cells and direct contact between different cell types have been developed that expand upon simple co-culture methods, specific control over heterojunctions that form between cells is not easily accomplished with current methods, such as 3D cell-printing. In this article, DNA-mediated cell interactions are combined with cell-compatible photolithographic approaches to control cell assembly. Specifically, cells are coated with oligonucleotides containing DNA nucleobases that are protected with photocleavable moieties; this coating facilitated light-controlled cell assembly when these cells were mixed with cells coated with complementary oligonucleotides. By combining this technology with digital micromirror devices mounted on a microscope, selective activation of specific cell populations for interactions with other cells was achieved. Importantly, this technique is rapid and uses non-UV light sources. Taken together, this technique opens new pathways for on-demand programming of complex cell structures.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 4","pages":"386–393"},"PeriodicalIF":0.0,"publicationDate":"2023-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44615029","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":"Stable Uranium Oxide Under Atmospheric Conditions: An Electroplating Technique for U Film Fabrication at Boron-Doped Diamond Electrodes","authors":"Armando Peña-Duarte,&nbsp;Alexis J. Acevedo-González,&nbsp;Richard M. Lagle,&nbsp;Mebougna Drabo,&nbsp;Stephen U. Egarievwe and Carlos R. Cabrera*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00007","DOIUrl":"10.1021/acsmaterialsau.3c00007","url":null,"abstract":"<p >An electrodeposition technique of low-enriched uranium onto boron-doped diamond (BDD) electrodes for uranium electro-assembling, sequestration, uranium electrowinning (as the electroextraction alternative), and future neutron detection applications has been developed. Our findings through physicochemical characterization and an in-depth XPS analysis show that the U/BDD system consists of a blend of uranium oxides with IV, V, and VI oxidation states. Results show that U⁵⁺ is present and stable under open atmospheric conditions. The U electrodeposition on BDD creates smooth surfaces, free of voids, with uniform deposition of homogeneous tiny particles of stable uranium oxides, instead of chunky particles, and uranium compound mixtures, like large fibers of the precursor uranyl. Our electrochemical method operates without high temperatures or hazardous compounds. Uranium corrosion and oxidation processes occur spontaneously and parallel to the electrochemical formation of metallic uranium on BDD electrode surfaces, with metallic uranium reacting with water, producing fine particles of UO₂. This work represents the first attempt to create a surface of uranium oxides, where the film thickness can be controlled for future applications, <i>e.g.</i>, improving sensitivity in neutron detection technologies. Our U electro-assembling method provides a sustainable strategy for uranium electro-recovery from nuclear wastes, immobilizing uranium as a storage method or as U-film fabrication (U/BDD) for future neutron detection applications. Besides, this work contributes to uranium-based technologies, improving them and providing a better understanding of their electrochemical properties, <i>e.g.</i>, uranium redox processes, uranium oxides’ formation, and stability evaluation. These properties are of remarkable need for uranium-based target formation. The use of our U/BDD method is proposed as an environmental protocol to recover and immobilize uranium-235, and other fissile materials, from civil and defense wastes, contaminated systems, and stockpiles.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 4","pages":"351–359"},"PeriodicalIF":0.0,"publicationDate":"2023-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45555590","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":"Cell-Sized Confinements Alter Molecular Diffusion in Concentrated Polymer Solutions Due to Length-Dependent Wetting of Polymers","authors":"Yuki Kanakubo,&nbsp;Chiho Watanabe,&nbsp;Johtaro Yamamoto,&nbsp;Naoya Yanagisawa,&nbsp;Hiroki Sakuta,&nbsp;Arash Nikoubashman* and Miho Yanagisawa*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00018","DOIUrl":"10.1021/acsmaterialsau.3c00018","url":null,"abstract":"<p >Living cells are characterized by the micrometric confinement of various macromolecules at high concentrations. Using droplets containing binary polymer blends as artificial cells, we previously showed that cell-sized confinement causes phase separation of the binary polymer solutions because of the length-dependent wetting of the polymers. Here, we demonstrate that the confinement-induced heterogeneity of polymers also emerges in single-component polymer solutions. The resulting structural heterogeneity also leads to a slower transport of small molecules at the center of cell-sized droplets than that in bulk solutions. Coarse-grained molecular simulations support this confinement-induced heterogeneous distribution by polymer length and demonstrate that the effective wetting of the shorter chains at the droplet surface originates from the length-dependent conformational entropy. Our results suggest that cell-sized confinement functions as a structural regulator for polydisperse polymer solutions that specifically manipulates the diffusion of molecules, particularly those with sizes close to the correlation length of the polymer chains.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"3 5","pages":"442–449"},"PeriodicalIF":0.0,"publicationDate":"2023-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00018","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43430831","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}