Materials Science Surfaces, Coatings and Films

Polymer Surface Interaction Studies

Description

This cluster of papers focuses on the development and application of mussel-inspired surface chemistry for multifunctional coatings. It covers topics such as polydopamine and its derivatives, antifouling coatings, biomedical applications, polymer brushes, layer-by-layer assembly, protein adsorption, zwitterionic materials, and self-assembled monolayers.

Keywords

Mussel-Inspired; Surface Chemistry; Polydopamine; Antifouling Coatings; Biomedical Applications; Polymer Brushes; Layer-by-Layer Assembly; Protein Adsorption; Zwitterionic Materials; Self-Assembled Monolayers

Thin-film fabrication The deposition of thin films from multiple materials is essential to a range of materials fabrication processes. Layer-by-layer processes involve the sequential deposition of two or more materials … Thin-film fabrication The deposition of thin films from multiple materials is essential to a range of materials fabrication processes. Layer-by-layer processes involve the sequential deposition of two or more materials that physically bond together. Richardson et al. review some of the techniques and materials that are used to make thin films, including sequential dip coating, spraying, and electrochemical deposition. Despite the versatility of the methods and the range of materials that can be deposited, the techniques remain mostly confined to the lab because of challenges in industrial scaling. But because there is tremendous scope for fine-tuning the structure and properties of the multilayers, there is interest in broadening the use of these techniques. Science , this issue 10.1126/science.aaa2491
The dependence of polyelectrolyte multilayer thickness on salt concentration, salt type, solvent quality, deposition time, and polymer concentration is evaluated. Polymers are deposited on spinning silicon wafers. For the strong … The dependence of polyelectrolyte multilayer thickness on salt concentration, salt type, solvent quality, deposition time, and polymer concentration is evaluated. Polymers are deposited on spinning silicon wafers. For the strong polycation/polyanion pair studied, film thickness is approximately proportional to the number of layers and the salt concentration. The irreversibility of overall molecule adsorption is indicated by the lack of exchange of surface (radiolabeled) for solution polymer. The hydrophobic nature of the driving force for polymer sorption is illustrated by the choice of salt counterion or solvent. Analyzed within the framework of ion exchange, the net energy of ion pair formation is not high, at most a few kT. Salt, competing with polymer segments for the surface, permits localized rearrangements. In the mechanism proposed, excess polymer is accommodated within several layers, rather than in one layer of loops and tails. Steric barriers coupled with slow conformational changes are responsible for long-term polymer adsorption. Considering the disorder and interpenetration, multilayer buildup has much in common with solution phase or coprecipitated polyelectrolyte complexes. Surface hydrophobicity can be enhanced using fluorinated surfactants as counterions.
The development of facile and versatile strategies for thin-film and particle engineering is of immense scientific interest. However, few methods can conformally coat substrates of different composition, size, shape, and … The development of facile and versatile strategies for thin-film and particle engineering is of immense scientific interest. However, few methods can conformally coat substrates of different composition, size, shape, and structure. We report the one-step coating of various interfaces using coordination complexes of natural polyphenols and Fe(III) ions. Film formation is initiated by the adsorption of the polyphenol and directed by pH-dependent, multivalent coordination bonding. Aqueous deposition is performed on a range of planar as well as inorganic, organic, and biological particle templates, demonstrating an extremely rapid technique for producing structurally diverse, thin films and capsules that can disassemble. The ease, low cost, and scalability of the assembly process, combined with pH responsiveness and negligible cytotoxicity, makes these films potential candidates for biomedical and environmental applications.
Abstract The design of advanced, nanostructured materials at the molecular level is of tremendous interest for the scientific and engineering communities because of the broad application of these materials in … Abstract The design of advanced, nanostructured materials at the molecular level is of tremendous interest for the scientific and engineering communities because of the broad application of these materials in the biomedical field. Among the available techniques, the layer‐by‐layer assembly method introduced by Decher and co‐workers in 1992 has attracted extensive attention because it possesses extraordinary advantages for biomedical applications: ease of preparation, versatility, capability of incorporating high loadings of different types of biomolecules in the films, fine control over the materials' structure, and robustness of the products under ambient and physiological conditions. In this context, a systematic review of current research on biomedical applications of layer‐by‐layer assembly is presented. The structure and bioactivity of biomolecules in thin films fabricated by layer‐by‐layer assembly are introduced. The applications of layer‐by‐layer assembly in biomimetics, biosensors, drug delivery, protein and cell adhesion, mediation of cellular functions, and implantable materials are addressed. Future developments in the field of biomedical applications of layer‐by‐layer assembly are also discussed.
A detailed study of the role that solution pH plays in the layer-by-layer processing of the weak polyelectrolytes poly(acrylic acid) and poly(allylamine hydrochoride) was carried out. It was found that … A detailed study of the role that solution pH plays in the layer-by-layer processing of the weak polyelectrolytes poly(acrylic acid) and poly(allylamine hydrochoride) was carried out. It was found that dramatically different polymer adsorption behavior is observed as one systematically increases (or decreases) the charge density of a weak polyelectrolyte including transitions from very thick adsorbed layers (ca. 80 Å) to very thin adsorbed layers (ca. 4 Å) over a very narrow pH range. By controlling pH, it is possible to vary the thickness of an adsorbed polycation or polyanion layer from 5 to 80 Å. In addition, control over the bulk and surface composition of the resultant multilayer thin films is readily achieved via simple pH adjustments. These studies have provided new insights into the polyelectrolyte sequential adsorption process and have already opened up some interesting technological applications.
The amount of plasma protein adsorbed on a phospholipid polymer having a 2-methacryloyloxyethyl phosphorylcholine (MPC) moiety was reduced compared to the amount of protein adsorbed onto poly[2-hydroxyethyl methacrylate (HEMA)], poly[n-butyl … The amount of plasma protein adsorbed on a phospholipid polymer having a 2-methacryloyloxyethyl phosphorylcholine (MPC) moiety was reduced compared to the amount of protein adsorbed onto poly[2-hydroxyethyl methacrylate (HEMA)], poly[n-butyl methacrylate (BMA)], and BMA copolymers with acrylamide (AAm) or N-vinyl pyrrolidone (VPy) moieties having a hydrophilic fraction. To clarify the reason for the reduced protein adsorption on the MPC polymer, the water structure in the hydrated polymer was examined with attention to the free water fraction. Hydration of the polymers occurred when they were immersed in water. The differential scanning calorimetric analysis of these hydrated polymers revealed that the free water fractions in the poly(MPC-co-BMA) and poly(MPC-co-n-dodecyl methacrylate) with a 0.30 MPC mole fraction were above 0.70. On the other hand, the free water fractions in the poly(HEMA), poly(AAm-co-BMA), and poly(VPy-co-BMA) were below 0.42. The conformational change in proteins adsorbed on the MPC polymers and poly(HEMA) were determined using ultraviolet and circular dichroism spectroscopic measurements. Proteins adsorbed on poly(HEMA) changed considerably, but those adsorbed on poly(MPC-co-BMA) with a 0.30 MPC mole fraction differed little from the native state. We concluded from these results that fewer proteins are adsorbed and their original conformation is not changed on polymer surfaces that possess a high free water fraction. © 1998 John Wiley & Sons, Inc. J Biomed Mater Res, 39, 323–330, 1998.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAdsorption of proteins onto surfaces containing end-attached oligo(ethylene oxide): a model system using self-assembled monolayersKevin L. Prime and George M. WhitesidesCite this: J. Am. Chem. Soc. 1993, … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAdsorption of proteins onto surfaces containing end-attached oligo(ethylene oxide): a model system using self-assembled monolayersKevin L. Prime and George M. WhitesidesCite this: J. Am. Chem. Soc. 1993, 115, 23, 10714–10721Publication Date (Print):November 1, 1993Publication History Published online1 May 2002Published inissue 1 November 1993https://pubs.acs.org/doi/10.1021/ja00076a032https://doi.org/10.1021/ja00076a032research-articleACS PublicationsRequest reuse permissionsArticle Views6525Altmetric-Citations1439LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts
Hollow silica and silica-polymer spheres with diameters between 720 and 1000 nanometers were fabricated by consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either … Hollow silica and silica-polymer spheres with diameters between 720 and 1000 nanometers were fabricated by consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either by calcination or decomposition upon exposure to solvents. Scanning and transmission electron microscopy images demonstrate that the wall thickness of the hollow spheres can be readily controlled by varying the number of nanoparticle-polymer deposition cycles, and the size and shape are determined by the morphology of the templating colloid. The hollow spheres produced are envisioned to have applications in areas ranging from medicine to pharmaceutics to materials science.
Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) … Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) Advances in Insect Physiology: Insect Integument and Color , eds Jérôme C, Stephen JS (Academic Press, London), pp 75–133]. Coordination between Fe and catechol ligands has recently been correlated to the hardness and high extensibility of the cuticle of mussel byssal threads and proposed to endow self-healing properties [Harrington MJ, Masic A, Holten-Andersen N, Waite JH, Fratzl P (2010) Science 328:216–220]. Inspired by the pH jump experienced by proteins during maturation of a mussel byssus secretion, we have developed a simple method to control catechol-Fe 3+ interpolymer cross-linking via pH. The resonance Raman signature of catechol-Fe 3+ cross-linked polymer gels at high pH was similar to that from native mussel thread cuticle and the gels displayed elastic moduli (G′) that approach covalently cross-linked gels as well as self-healing properties.
Protein adhesion plays a major role in determining the biocompatibility of materials. The first stage of implant integration is the adhesion of protein followed by cell attachment. Surface modification of … Protein adhesion plays a major role in determining the biocompatibility of materials. The first stage of implant integration is the adhesion of protein followed by cell attachment. Surface modification of implants (surface chemistry and topography) to induce and control protein and cell adhesion is currently of great interest. This communication presents data on protein adsorption (bovine serum albumin and fibrinogen) onto model hydrophobic (CH3) and hydrophilic (OH) surfaces, investigated using a quartz crystal microbalance (QCM) and grazing angle infrared spectroscopy. Our data suggest that albumin undergoes adsorption via a single step whereas fibrinogen adsorption is a more complex, multistage process. Albumin has a stronger affinity toward the CH3 compared to OH terminated surface. In contrast, fibrinogen adheres more rapidly to both surfaces, having a slightly higher affinity toward the hydrophobic surface. Conformational assessment of the adsorbed proteins by grazing angle infrared spectroscopy (GA-FTIR) shows that after an initial 1 h incubation few further time-dependent changes are observed. Both proteins exhibited a less organized secondary structure upon adsorption onto a hydrophobic surface than onto a hydrophilic surface, with the effect observed greatest for albumin. This study demonstrates the ability of simple tailor-made monochemical surfaces to influence binding rates and conformation of bound proteins through protein−surface interactions. Current interest in biocompatible materials has focused on surface modifications to induce rapid healing, both of implants and for wound care products. This effect may also be of significance at the next stage of implant integration, as cell adhesion occurs through the surface protein layer.
Abstract New frontiers in materials and polymer science include the development of assembly processes that are flexible, allow the access and implementation of nanoscale structure and order, can provide access … Abstract New frontiers in materials and polymer science include the development of assembly processes that are flexible, allow the access and implementation of nanoscale structure and order, can provide access to a broad range of materials systems, and yet can be implemented at relatively low cost. The ability to fine tune the composition of nanostructured thin films on the nanometer length scale, when combined with inexpensive patterning and templating routes, provides a powerful tool for nano‐ and microscale assembly of devices and novel new material systems. The layer‐by‐layer electrostatic assembly technique is a rich, versatile, and significantly inexpensive approach to the formation of thin films via alternating adsorption of positively and negatively charged species from aqueous solutions; this method has also been extended to include the alternation of polymers with hydrogen‐bond donor and acceptor groups. Polymer organic and organic/inorganic thin films formed using this technique may contain a number of different functional groups, including electro‐optic, electroluminescent, conducting, and dielectric layers, and functional organic and inorganic nanoparticles. Newly developed materials systems based on alternating layer methods will be addressed, as well as a number of frontier areas and future areas for the use of these systems, ranging from nanomechanical composites to electrochemical devices and templated deposition of functional microspheres. Both new functionalities incorporated within these materials and new means of patterning and templating these structures in two and three dimensions will be addressed in this review.
Surface resistance to nonspecific protein adsorption, cell/bacterial adhesion, and biofilm formation is critical for the development and performance of biomedical and analytical devices. Significant needs and efforts have been made … Surface resistance to nonspecific protein adsorption, cell/bacterial adhesion, and biofilm formation is critical for the development and performance of biomedical and analytical devices. Significant needs and efforts have been made in the development of biocompatible and bioactive materials for antifouling surfaces, but much of the work retains an empirical flavor due to the complexity of experiments and the lack of robust theoretical models. In this review, two major classes of nonfouling materials (i.e. hydrophilic and zwitterionic materials) and associated basic nonfouling mechanisms and practical examples are discussed. Highly hydrated chemical groups with optimized physical properties of the surface, along with appropriate surface coating methods, are the keys to developing effective and stable nonfouling materials for long-term biomedical applications. The zwitterionic polymers are promising nonfouling biomaterials due to the simplicity of synthesis, ease of applicability, abundance of raw materials, and availability of functional groups.
ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPolymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and ApplicationsRaphael Barbey, Laurent Lavanant, Dusko Paripovic, Nicolas Schüwer, Caroline Sugnaux, Stefano Tugulu, and Harm-Anton Klok*View Author … ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPolymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and ApplicationsRaphael Barbey, Laurent Lavanant, Dusko Paripovic, Nicolas Schüwer, Caroline Sugnaux, Stefano Tugulu, and Harm-Anton Klok*View Author Information École Polytechnique Fédérale de Lausanne (EPFL), Institut des Matériaux, Laboratoire des Polymères, Bâtiment MXD, Station 12, CH-1015 Lausanne, Switzerland* To whom correspondence should be addressed. E-mail: [email protected]. Fax: +41 21 693 5650. Telephone: +41 21 693 4866.Cite this: Chem. Rev. 2009, 109, 11, 5437–5527Publication Date (Web):October 21, 2009Publication History Received5 February 2009Published online21 October 2009Published inissue 11 November 2009https://pubs.acs.org/doi/10.1021/cr900045ahttps://doi.org/10.1021/cr900045areview-articleACS PublicationsCopyright © 2009 American Chemical SocietyRequest reuse permissionsArticle Views39655Altmetric-Citations1562LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Organic compounds,Polymer brushes,Polymers,Radical polymerization,Silicon Get e-Alerts
Nanomaterials hold promise as multifunctional diagnostic and therapeutic agents. However, the effective application of nanomaterials is hampered by limited understanding and control over their interactions with complex biological systems. When … Nanomaterials hold promise as multifunctional diagnostic and therapeutic agents. However, the effective application of nanomaterials is hampered by limited understanding and control over their interactions with complex biological systems. When a nanomaterial enters a physiological environment, it rapidly adsorbs proteins forming what is known as the protein 'corona'. The protein corona alters the size and interfacial composition of a nanomaterial, giving it a biological identity that is distinct from its synthetic identity. The biological identity determines the physiological response including signalling, kinetics, transport, accumulation, and toxicity. The structure and composition of the protein corona depends on the synthetic identity of the nanomaterial (size, shape, and composition), the nature of the physiological environment (blood, interstitial fluid, cell cytoplasm, etc.), and the duration of exposure. In this critical review, we discuss the formation of the protein corona, its structure and composition, and its influence on the physiological response. We also present an 'adsorbome' of 125 plasma proteins that are known to associate with nanomaterials. We further describe how the protein corona is related to the synthetic identity of a nanomaterial, and highlight efforts to control protein-nanomaterial interactions. We conclude by discussing gaps in the understanding of protein-nanomaterial interactions along with strategies to fill them (167 references).
Abstract Polydopamine is the first adhesive polymer that can functionalize surfaces made of virtually all material chemistries. The material‐independent surface modification properties of polydopamine allow the functionalization of various types … Abstract Polydopamine is the first adhesive polymer that can functionalize surfaces made of virtually all material chemistries. The material‐independent surface modification properties of polydopamine allow the functionalization of various types of medical and energy devices. However, the mechanism of dopamine polymerization has not yet been clearly demonstrated. Covalent oxidative polymerization via 5,6‐dihydroxyindole (DHI), which is similar to the mechanism for synthetic melanin synthesis, has been the clue. Here, it is reported that a physical, self‐assembled trimer of (dopamine) 2 /DHI exists in polydopamine, which has been known to be formed only by covalent polymerization. It is also found that the trimeric complex is tightly entrapped within polydopamine and barely escapes from the polydopamine complex. The result explains the previously reported in vitro and in vivo biocompatibility. The study reveals a different perspective of polydopamine formation, where it forms in part by the self‐assembly of dopamine and DHI, providing a new clue toward understanding the structures of catecholamines such as melanin.
Exact control of the film thickness of polyelectrolyte shells (a transmission electron microscopy image is shown) is achieved by colloid-templated consecutive adsorption of polyanions and polycations followed by decomposition of … Exact control of the film thickness of polyelectrolyte shells (a transmission electron microscopy image is shown) is achieved by colloid-templated consecutive adsorption of polyanions and polycations followed by decomposition of the templating core. Possible areas of application for these shells range from the pharmaceutical, food, cosmetic, and paint industries to catalysis and microcrystallization.
An appropriate cellular response to implanted surfaces is essential for tissue regeneration and integration. It is well described that implanted materials are immediately coated with proteins from blood and interstitial … An appropriate cellular response to implanted surfaces is essential for tissue regeneration and integration. It is well described that implanted materials are immediately coated with proteins from blood and interstitial fluids, and it is through this adsorbed layer that cells sense foreign surfaces. Hence, it is the adsorbed proteins, rather than the surface itself, to which cells initially respond. Diverse studies using a range of materials have demonstrated the pivotal role of extracellular adhesion proteins—fibronectin and vitronectin in particular—in cell adhesion, morphology, and migration. These events underlie the subsequent responses required for tissue repair, with the nature of cell surface interactions contributing to survival, growth, and differentiation. The pattern in which adhesion proteins and other bioactive molecules adsorb thus elicits cellular reactions specific to the underlying physicochemical properties of the material. Accordingly, in vitro studies generally demonstrate favorable cell responses to charged, hydrophilic surfaces, corresponding to superior adsorption and bioactivity of adhesion proteins. This review illustrates the mediation of cell responses to biomaterials by adsorbed proteins, in the context of osteoblasts and selected materials used in orthopedic implants and bone tissue engineering. It is recognized, however, that the periimplant environment in vivo will differ substantially from the cell–biomaterial interface in vitro. Hence, one of the key issues yet to be resolved is that of the interface composition actually encountered by osteoblasts within the sequence of inflammation and bone regeneration.
In this work, we show the strong resistance of zwitterionic phosphorylcholine (PC) self-assembled monolayers (SAMs) to protein adsorption and examine key factors leading to their nonfouling behavior using both experimental … In this work, we show the strong resistance of zwitterionic phosphorylcholine (PC) self-assembled monolayers (SAMs) to protein adsorption and examine key factors leading to their nonfouling behavior using both experimental and molecular simulation techniques. Zwitterions with a balanced charge and minimized dipole are excellent candidates as nonfouling materials due to their strong hydration capacity via electrostatic interactions.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTheory of the grafted polymer brushS. T. Milner, T. A. Witten, and M. E. CatesCite this: Macromolecules 1988, 21, 8, 2610–2619Publication Date (Print):August 1, 1988Publication History Published … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTheory of the grafted polymer brushS. T. Milner, T. A. Witten, and M. E. CatesCite this: Macromolecules 1988, 21, 8, 2610–2619Publication Date (Print):August 1, 1988Publication History Published online1 May 2002Published inissue 1 August 1988https://pubs.acs.org/doi/10.1021/ma00186a051https://doi.org/10.1021/ma00186a051research-articleACS PublicationsRequest reuse permissionsArticle Views8421Altmetric-Citations1328LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
In recent years, zwitterionic materials such as poly(carboxybetaine) (pCB) and poly(sulfobetaine) (pSB) have been applied to a broad range of biomedical and engineering materials. Due to electrostatically induced hydration, surfaces … In recent years, zwitterionic materials such as poly(carboxybetaine) (pCB) and poly(sulfobetaine) (pSB) have been applied to a broad range of biomedical and engineering materials. Due to electrostatically induced hydration, surfaces coated with zwitterionic groups are highly resistant to nonspecific protein adsorption, bacterial adhesion, and biofilm formation. Among zwitterionic materials, pCB is unique due to its abundant functional groups for the convenient immobilization of biomolecules. pCB can also be prepared in a hydrolyzable form as cationic pCB esters, which can kill bacteria or condense DNA. The hydrolysis of cationic pCB esters into nonfouling zwitterionic groups will lead to the release of killed microbes or the irreversible unpackaging of DNA. Furthermore, mixed-charge materials have been shown to be equivalent to zwitterionic materials in resisting nonspecific protein adsorption when they are uniformly mixed at the molecular scale.
A new surface bioconjugation strategy is presented. A polydopamine surface coating provides chemical activation on material surfaces, is resistant to hydrolysis, and offers selectivity in coupling of biomolecules via nucleophilic … A new surface bioconjugation strategy is presented. A polydopamine surface coating provides chemical activation on material surfaces, is resistant to hydrolysis, and offers selectivity in coupling of biomolecules via nucleophilic groups through simple pH control. Control of orientation of immobilized biomolecules may be possible using terminally modified DNA or His-containing proteins. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTColloid stabilization with grafted polyelectrolytesPhilip PincusCite this: Macromolecules 1991, 24, 10, 2912–2919Publication Date (Print):May 1, 1991Publication History Published online1 May 2002Published inissue 1 May 1991https://pubs.acs.org/doi/10.1021/ma00010a043https://doi.org/10.1021/ma00010a043research-articleACS PublicationsRequest reuse … ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTColloid stabilization with grafted polyelectrolytesPhilip PincusCite this: Macromolecules 1991, 24, 10, 2912–2919Publication Date (Print):May 1, 1991Publication History Published online1 May 2002Published inissue 1 May 1991https://pubs.acs.org/doi/10.1021/ma00010a043https://doi.org/10.1021/ma00010a043research-articleACS PublicationsRequest reuse permissionsArticle Views3246Altmetric-Citations870LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
A simple technique for precisely controlling the interfacial energies and wetting behavior of polymers in contact with solid surfaces is described. End-functionalized statistical random copolymers of styrene and methylmethacrylate were … A simple technique for precisely controlling the interfacial energies and wetting behavior of polymers in contact with solid surfaces is described. End-functionalized statistical random copolymers of styrene and methylmethacrylate were synthesized, with the styrene fraction f varying from 0 to 1, and were end-grafted onto silicon substrates to create random copolymer brushes about 5 nanometers thick. For f < 0.7, polystyrene (PS) films (20 nanometers thick) rapidly dewet from the brushes when heated well above the glass transition temperature. The contact angle of the resulting polymer droplets increased monotonically with decreasing f . Similar behavior was observed for poly(methylmethacrylate) (PMMA) films but with an opposite dependence on f . The interfacial energies of the random copolymer brushes with PS and PMMA were equal when f was about 0.6. Thus, precise control of the relative surface affinities of PS and PMMA was possible, demonstrating a way to manipulate polymer-surface interactions.
We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we … We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules.
Hydrophilic nanoparticulate carriers have important potential applications for the administration of therapeutic molecules. The recently developed hydrophobic-hydrophilic carriers require the use of organic solvents for their preparation and have a … Hydrophilic nanoparticulate carriers have important potential applications for the administration of therapeutic molecules. The recently developed hydrophobic-hydrophilic carriers require the use of organic solvents for their preparation and have a limited protein-loading capacity. To address these limitations a new approach for the preparation of nanoparticles made solely of hydrophilic polymers is presented. The preparation technique, based on an ionic gelation process, is extremely mild and involves the mixture of two aqueous phases at room temperature. One phase contains the polysaccharide chitosan (CS) and a diblock copolymer of ethylene oxide and propylene oxide (PEO-PPO) and, the other, contains the polyanion sodium tripolyphosphate (TPP). Size (200–1000 nm) and zeta potential (between +20 mV and +60 mV) of nanoparticles can be conveniently modulated by varying the ratio CS/PEO-PPO. Furthermore, using bovine serum albumin (BSA) as a model protein it was shown that these new nanoparticles have a great protein loading capacity (entrapment efficiency up to 80% of the protein) and provide a continuous release of the entrapped protein for up to 1 week. © 1997 John Wiley & Sons, Inc.
Multilayer films of organic compounds on solid surfaces have been studied for more than 60 years because they allow fabrication of multicomposite molecular assemblies of tailored architecture. However, both the … Multilayer films of organic compounds on solid surfaces have been studied for more than 60 years because they allow fabrication of multicomposite molecular assemblies of tailored architecture. However, both the Langmuir-Blodgett technique and chemisorption from solution can be used only with certain classes of molecules. An alternative approach—fabrication of multilayers by consecutive adsorption of polyanions and polycations—is far more general and has been extended to other materials such as proteins or colloids. Because polymers are typically flexible molecules, the resulting superlattice architectures are somewhat fuzzy structures, but the absence of crystallinity in these films is expected to be beneficial for many potential applications.
Keeping drugs under control: Hydrothermally stable, hollow mesoporous silica spheres have a high drug storage capacity, and polyelectrolyte multilayers coated on the spheres act as a switch for drug release … Keeping drugs under control: Hydrothermally stable, hollow mesoporous silica spheres have a high drug storage capacity, and polyelectrolyte multilayers coated on the spheres act as a switch for drug release which is controlled by the pH or ionic strength of the release medium. The picture shows the release of ibuprofen (IBU) from spheres with and without coatings of sodium polystyrene sulfonate (PSS) and poly(allylamine hydrochloride) (PAH). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z501500_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
This study investigates alginate−chitosan polyelectrolyte complexes (PECs) in the form of a film, a precipitate, as well as a layer-by-layer (LbL) assembly. The focus of this study is to fully … This study investigates alginate−chitosan polyelectrolyte complexes (PECs) in the form of a film, a precipitate, as well as a layer-by-layer (LbL) assembly. The focus of this study is to fully characterize, using the complementary techniques of Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) in combination with solution stability evaluation, the interactions between alginate and chitosan in the PECs. In the FTIR spectra, no significant change in the band position of the two carbonyl vibrations from alginate occurs upon interaction with different ionic species. However, protonation of the carboxylate group causes a new band to appear at 1710 cm-1, as anticipated. Partial protonation of the amine group of chitosan causes the appearance of one new band (∼1530 cm-1) due to one of the −NH3+ vibrational modes (the other mode overlaps the amide I band). Importantly, the position of the two main bands in the spectral region of interest in partly protonated chitosan films is not dependent on the extent of protonation. XPS N 1s narrow scans can, however, be used to assess the degree of amine protonation. In our alginate−chitosan film, precipitate, and LbL assembly, the bands observed in the FTIR correspond to the species −COO- and −NH3+, but their position is not different from each of the single components. Thus, the conclusion of the study is that FTIR cannot be used directly to identify the presence of PECs. However, in combination with XPS (survey and narrow N 1s scans) and solution stability evaluation, a more complete description of the structure can be obtained. This conclusion challenges the assignment of FTIR spectra in the literature.
Polymer brushes produced by controlled surface-initiated polymerization provide a route to surfaces coated with well-defined thin polymer films that are covalently bound to the substrate. All of the major controlled … Polymer brushes produced by controlled surface-initiated polymerization provide a route to surfaces coated with well-defined thin polymer films that are covalently bound to the substrate. All of the major controlled polymerization techniques have been applied to the synthesis of polymer brushes and examples of each are presented here. Many examples of brush synthesis in the literature have used the living atom transfer radical polymerization (ATRP) system, and in this tutorial review a particular focus is given to examples of this technique.
Mussels attach to solid surfaces in the sea. Their adhesion must be rapid, strong, and tough, or else they will be dislodged and dashed to pieces by the next incoming … Mussels attach to solid surfaces in the sea. Their adhesion must be rapid, strong, and tough, or else they will be dislodged and dashed to pieces by the next incoming wave. Given the dearth of synthetic adhesives for wet polar surfaces, much effort has been directed to characterizing and mimicking essential features of the adhesive chemistry practiced by mussels. Studies of these organisms have uncovered important adaptive strategies that help to circumvent the high dielectric and solvation properties of water that typically frustrate adhesion. In a chemical vein, the adhesive proteins of mussels are heavily decorated with Dopa, a catecholic functionality. Various synthetic polymers have been functionalized with catechols to provide diverse adhesive, sealant, coating, and anchoring properties, particularly for critical biomedical applications.
This review addresses the fabrication and properties of novel polyelectrolyte microcapsules, with an emphasis on their mechanical and permeability properties. Ease of preparation through layer-by-layer self assembly, accurate control over … This review addresses the fabrication and properties of novel polyelectrolyte microcapsules, with an emphasis on their mechanical and permeability properties. Ease of preparation through layer-by-layer self assembly, accurate control over wall thickness as well as flexibility in the choice of constituents make these capsules very promising for numerous applications in materials and life science. Moreover, by engineering the inner and outer interfaces, these capsules can be used as microreactors for precipitation, crystallization, and polymerization reactions, as well as enzymatic, and heterogeneous catalysis.
The attachment strategy based on catecholic chemistry has been arousing renewed interest since the work on polymerized catecholic amine (polydopamine) (Messersmith et al., Science, 2007, 318, 426) was published. Catechols … The attachment strategy based on catecholic chemistry has been arousing renewed interest since the work on polymerized catecholic amine (polydopamine) (Messersmith et al., Science, 2007, 318, 426) was published. Catechols and their derived compounds can self-assemble on various inorganic and organic materials, including noble metals, metals, metal oxides, mica, silica, ceramics and even polymers. It opens a new route to the modification of various substrates and the preparation of functional composite materials by simple chemistry. However, there is still not a full review so far about the attachment chemistry despite the dramatically increasing number of publications. This critical review describes the state-of-the-art research in the area: the design and synthesis of catecholic molecules, their adsorption mechanisms and the stability of assemblies in solution, and their applications etc. Some perspectives on future development are raised (195 references).
ADVERTISEMENT RETURN TO ISSUEArticleNEXTWater Gelation by Small Organic MoleculesLara A. Estroff and Andrew D. HamiltonView Author Information Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107 Cite … ADVERTISEMENT RETURN TO ISSUEArticleNEXTWater Gelation by Small Organic MoleculesLara A. Estroff and Andrew D. HamiltonView Author Information Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107 Cite this: Chem. Rev. 2004, 104, 3, 1201–1218Publication Date (Web):February 21, 2004Publication History Received10 April 2003Published online21 February 2004Published inissue 1 March 2004https://pubs.acs.org/doi/10.1021/cr0302049https://doi.org/10.1021/cr0302049research-articleACS PublicationsCopyright © 2004 American Chemical SocietyRequest reuse permissionsArticle Views16892Altmetric-Citations1885LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aggregation,Fibers,Gelation,Hydrophobicity,Molecules Get e-Alerts
Polydopamine is one of the simplest and most versatile approaches to functionalizing material surfaces, having been inspired by the adhesive nature of catechols and amines in mussel adhesive proteins. Since … Polydopamine is one of the simplest and most versatile approaches to functionalizing material surfaces, having been inspired by the adhesive nature of catechols and amines in mussel adhesive proteins. Since its first report in 2007, a decade of studies on polydopamine molecular structure, deposition conditions, and physicochemical properties have ensued. During this time, potential uses of polydopamine coatings have expanded in many unforeseen directions, seemingly only limited by the creativity of researchers seeking simple solutions to manipulating surface chemistry. In this review, we describe the current state of the art in polydopamine coating methods, describe efforts underway to uncover and tailor the complex structure and chemical properties of polydopamine, and identify emerging trends and needs in polydopamine research, including the use of dopamine analogs, nitrogen-free polyphenolic precursors, and improvement of coating mechanical properties.
Polymers attached by one end to an interface at relatively high coverage stretch away from the interface to avoid overlapping, forming a polymer "brush." This simple picture may serve as … Polymers attached by one end to an interface at relatively high coverage stretch away from the interface to avoid overlapping, forming a polymer "brush." This simple picture may serve as the basis for models in diverse interfacial systems in polymer science, such as polymeric surfactants, stabilized suspensions of colloidal particles, and structures formed by block copolymers. The structure and dynamics of polymer brushes have been the subject of considerable theoretical and experimental activity in recent years. An account is given of recent advances in theoretical understanding of stretched polymers at interfaces, and the diverse experimental probes of systems modeled by brushes are briefly reviewed.
Abstract Polyurethane (PU)‐silicone co‐polymers are increasingly favored in medical applications due to their excellent biostability and durability; however, their intrinsic hydrophobicity limits tissue integration. Polydopamine (PDA) deposition is a widely … Abstract Polyurethane (PU)‐silicone co‐polymers are increasingly favored in medical applications due to their excellent biostability and durability; however, their intrinsic hydrophobicity limits tissue integration. Polydopamine (PDA) deposition is a widely accepted method for increasing biomaterial surface hydrophilicity, though concentrations and methods vary across published literature. This study investigates the synergistic effects of PDA deposition and plasma oxidation on FDA‐approved Elast‐Eon E2A (E2A) to enhance cell attachment and wound healing. E2A substrates are treated with a range of plasma oxidation periods and PDA concentrations (0–5 min, 0‐0.5 w v−1% respectively). The combination of 0.05 w v−1% PDA and 1‐minute oxygen plasma results in the most significant reduction in water contact angle (92to 19°), increase in fibroblast adhesion (33.0–53.2 cells mm −2 ) and cell diameter, with an overall increase in intra‐ and extracellular collagen I and fibronectin. X‐ray photoelectron spectroscopy (XPS) reveals significant surface chemical changes, while surface roughness remains unchanged. Whole blood adhesion tests show no change in platelet adhesion or volume. These parameters may offer an improved approach for modifying PU‐copolymers to enhance cell interactions for use in current and future medical implants, including a suite of cardiovascular technologies that require both material ductility and rapid tissue integration.
ABSTRACT It remains challenging to graft polyacrylonitrile (PAN) brushes with thicknesses exceeding 15 nm from initiator‐functionalized silicon wafers via a controllable radical polymerization. Consequently, it isn't accessible to carry out … ABSTRACT It remains challenging to graft polyacrylonitrile (PAN) brushes with thicknesses exceeding 15 nm from initiator‐functionalized silicon wafers via a controllable radical polymerization. Consequently, it isn't accessible to carry out some research on their potential applications. To overcome this limitation, we employed a photo‐induced atom transfer radical polymerization (photo‐ATRP) technique to graft PAN brushes from the silicon wafer, with the polymerization process confined to microliter volumes between the substrate and a cover glass. Three classes of catalysts were explored for the feasibility to graft PAN brush. It was found that CuBr 2 combined with tris[2‐(dimethylamino)ethyl]amine (Me6‐TREN) shows promising performance. Subsequently, the effect of the CuBr 2 concentration, irradiation intensity, and monomer concentration on growth thickness of PAN brushes was systematically investigated. Our results revealed that the growth of PAN brush was highly sensitive to the variations of these parameters. Under optimized conditions, PAN brush films with more than 70 nm thickness were finally achieved, which were characterized by FT‐IR, XPS, and atomic force microscopy. Chain extension experiments further confirmed the living nature of the polymerization. Furthermore, we conducted preliminary investigations into the thickness‐dependent aggregation‐induced emission properties of the synthesized PAN brushes.
Polymer grafting density critically influences the self-assembly of polymer-grafted nanoparticles, yet the low grafting density regime remains underexplored. Here, we investigate the thin-film self-assembly of bottlebrush polymer-grafted core/shell nanoparticles (BPGNPs) … Polymer grafting density critically influences the self-assembly of polymer-grafted nanoparticles, yet the low grafting density regime remains underexplored. Here, we investigate the thin-film self-assembly of bottlebrush polymer-grafted core/shell nanoparticles (BPGNPs) under quasi-2D confinement at near-zero grafting densities through coarse-grained molecular dynamics (CGMD). The NP core is modeled using a hard-core/soft-shoulder (HCSS) potential, and it is compared against Weeks-Chandler-Andersen (WCA) potential. While the phase behaviors of both models are well-known, the distinct phase behaviors of both models persist even with polymer grafting offering additional room for tunability. Unlike sufficiently high grafting density or bare nanoparticles (NPs), grafting a single bottlebrush polymer breaks the rotational symmetry. The resulting structural polarity of grafted NPs can be precisely controlled through bottlebrush design parameters. We demonstrate that enhanced structural polarity stabilizes specific ordered phases, enabling precise control over self-assembled morphologies such as hexagonal lattices, square lattices, and linear clusters. Lastly, we explore the impact of synthesis-induced heterogeneity by introducing bare NPs, dual-polymer-grafted particles, and unconjugated polymers as minor species, providing insights into morphological stability under realistic grafting conditions. This work advances our understanding of BPGNP self-assembly in the near-zero grafting density regime and establishes design principles for functional nanotechnology applications.
ABSTRACT Polyelectrolyte brushes reorganize when they are placed in electric fields, which allows for a field‐induced collapse or swelling. While these systems have been studied theoretically in detail under salt‐free … ABSTRACT Polyelectrolyte brushes reorganize when they are placed in electric fields, which allows for a field‐induced collapse or swelling. While these systems have been studied theoretically in detail under salt‐free conditions, the effect of salt on the electroresponse has been less systematically explored. Yet, in potential applications, for example, for anti‐fouling, in biomedical systems or in the food industry, polyelectrolyte brushes are almost always in contact with solutions that contain salt. We use coarse‐grained molecular dynamic simulations and Scheutjens‐Fleer self‐consistent field theory to study the effect of salt on the electroresponse of two different polyelectrolyte brushes: a random copolymer of neutral and charged monomers and a gradient copolymer where the composition gradually changes from neutral at the grafting plane to charged at the free end. We find that salt only has a limited effect of the electroresponse when the brush is in the osmotic regime at low salt concentrations, while it stifles the response in the salted regime at high salt concentrations. Additionally, we find that the electroresponse in the transition between these regimes is significantly affected by chain architecture. Our results show that the electroresponse of polyelectrolyte brushes can still be used at salt concentrations as they occur in practical applications.
Enhancing the selectivity of endothelial cells (ECs) over smooth muscle cells (SMCs) on material surfaces is critical for improving the prognosis of cardiovascular device implantation, preventing restenosis, and avoiding late-stage … Enhancing the selectivity of endothelial cells (ECs) over smooth muscle cells (SMCs) on material surfaces is critical for improving the prognosis of cardiovascular device implantation, preventing restenosis, and avoiding late-stage thrombosis. However, existing surface modification strategies typically involve specific binding ligands such as antibodies and extracellular matrix peptides to promote EC adhesion, which exhibit low EC selectivity with EC/SMC ratios of less than 10. Herein, we report that an albumin coating, traditionally regarded as a bioinert surface lacking specific recognition functions, achieves unprecedented high EC selectivity with an EC/SMC ratio exceeding 200 in the medium supplemented with 5% fetal bovine serum. Mechanistic investigations reveal that this selectivity is achieved by selectively impeding the adhesion of SMCs, contrasting the traditional approach of using specific ligands to promote EC adhesion selectively. Evaluations in an animal model demonstrated successful inhibition of intimal hyperplasia and the promotion of endothelialization of the modified implants. This facile albumin modification shows potential for enhancing the performance of implantable cardiovascular devices by achieving complete endothelialization.
Polyelectrolyte microcapsules (PMCs) have a wide range of applications in fields such as medicine, pharmacology, diagnostics, etc., and can be used as targeted drug delivery vehicles, diagnostic systems and smart … Polyelectrolyte microcapsules (PMCs) have a wide range of applications in fields such as medicine, pharmacology, diagnostics, etc., and can be used as targeted drug delivery vehicles, diagnostic systems and smart materials. However, the existing research indicates that the type of core can influence the properties of the PMC shell. Consequently, we hypothesized that the type of core used for the formation of the PMC may also affect the desorption of the shell's polyelectrolytes. In this study, the desorption of polyelectrolytes of PMCs, formed on polystyrene cores (PMCPs) and MnCO3 (PMCMn) and CaCO3 cores (PMCCa), incubated in either NaCl or Na2SO4 solution, was investigated. It was demonstrated that the low ionic strength of the solution (up to 200 mM NaCl) has a negligible effect on the desorption of PMCCa. However, in the case of PMCPs and PMCMn, an increase in desorption was observed at 100 and 200 mM NaCl. Increasing the ionic strength to 1000 mM and 2000 mM resulted in a gradual increase in the desorption of the polyelectrolytes PMCCa and PMCMn, while for PMCPs, the maximum desorption was already observed at 1000 mM. Additionally, an increase in desorption was detected upon incubation in various concentrations of sodium sulfate (5-50 mM), although the desorption did not differ significantly across all types of PMCs. Nevertheless, for PMCMn, the maximum desorption was observed at a sodium sulfate concentration of 50 mM, whereas for other types of capsules, the maximum desorption occurred at a concentration of 100 mM. These results support the hypothesis that the type of core used in the formation of PMCs influences the desorption of the shell polyelectrolyte.
ABSTRACT Vascular restenosis, a significant complication after stent implantation, originates from the migration of vascular smooth muscle cells to the intima and the excessive extracellular matrix deposition, resulting in intimal … ABSTRACT Vascular restenosis, a significant complication after stent implantation, originates from the migration of vascular smooth muscle cells to the intima and the excessive extracellular matrix deposition, resulting in intimal hyperplasia. Thus, enhancing endothelial cell adhesion and reducing smooth muscle cell adhesion capacity are crucial to address this issue. Heparin, a naturally derived glycosaminoglycan, exhibits excellent anticoagulant activity and endothelial cell promoting effects, yet its clinical utility is constrained by bleeding risks, supply instability, immunogenicity, and demanding storage conditions. In this study, sulfonated carboxymethyl chitosan (SCCS) is employed as a heparin‐mimicking polymer, immobilized on a glass substrate via dopamine‐mediated adhesion. Compared with carboxymethyl chitosan, the SCCS‐coated substrate significantly promotes endothelial cell adhesion while effectively inhibiting smooth muscle cell attachment. Additionally, the whole blood cell analysis and complement activation results exhibit that the SCCS coating has excellent blood compatibility. These findings suggest that the SCCS coating has the potential to be applied on various vascular stents to prevent restenosis, offering a nobel strategy for improving vascular interventional therapy.
The translation of polymer brushes into technologically relevant coatings hinges on the development of scalable and robust fabrication strategies that are tolerant of environmental conditions. Surface-initiated photoinduced atom transfer radical … The translation of polymer brushes into technologically relevant coatings hinges on the development of scalable and robust fabrication strategies that are tolerant of environmental conditions. Surface-initiated photoinduced atom transfer radical polymerization (SI-photoATRP) has emerged as a powerful tool for synthesizing functional brushes with precise control over their architectural parameters. However, traditional SI-photoATRP requires high-energy light and confined setups to mitigate oxygen inhibition within nondeoxygenated mixtures, limiting substrate versatility and process scalability. Herein, we report a red-light-driven SI-photoATRP process enabled by a catalytic system composed of methylene blue (MB+) and a Cu-based ATRP catalyst, which achieves efficient polymer brush growth under fully open-air conditions. Systematic variation of reaction parameters─including light intensity, composition of the catalytic system, and solvent─enabled rapid growth of compositionally different brushes with high and tunable thickness. The deep penetration capability of red light was exploited to decorate microporous three-dimensional materials with polymer brushes. Spatially defined brush growth was demonstrated by shifting the wavelength of light irradiation, alternatively stimulating surface-initiated polymerization in the outer volumes of the support or uniformly across the entire microporous material.
Biomolecular condensates, or membraneless organelles, play pivotal roles in cellular organization by compartmentalizing biochemical reactions and regulating diverse processes such as RNA metabolism, signal transduction, and stress response. Super-resolved imaging … Biomolecular condensates, or membraneless organelles, play pivotal roles in cellular organization by compartmentalizing biochemical reactions and regulating diverse processes such as RNA metabolism, signal transduction, and stress response. Super-resolved imaging and single-molecule tracking are essential for probing the internal dynamics of these condensates, yet intrinsic Brownian (thermal capillary wave) motion of the entire condensate in vitro could introduce artifacts into diffusion measurements, confounding the interpretation of molecular mobility. Here, we systematically assess and address this question using both experiments and simulations. We deploy three surface-tethering strategies-using biotinylated DNA, protein, or antibody tethers-to immobilize FUS protein condensates on passivated glass surfaces. We show that tethering effectively suppresses the global translational and rotational Brownian motion of the entire condensate, eliminating inherent measurement artifacts while preserving their spherical appearance and native liquid-like properties. Quantitative analysis reveals that untethered condensates systematically overestimate or underestimate molecular diffusion coefficients and step sizes, particularly for slowly diffusing structured mRNAs, while rapidly diffusing unstructured RNAs are unaffected due to temporal scale separation. Comparative evaluation of tethering strategies demonstrates tunable control over condensate stability and internal dynamics, with implications for optimizing experimental design. Finally, simulations spanning the full physiological parameter space enable us to provide practical guidelines for assessing whether, and to what extent, tethering is beneficial, based on condensate size and the diffusion properties of the biomolecule of interest. Our findings establish surface tethering as a necessary and robust approach for accurate quantification of intra-condensate molecular dynamics, providing a methodological framework for future studies of membraneless organelles.
Simulated adsorption isotherms that describe the irreversible binding of cationic polydisperse polymers onto anionic porous wood pulp fibers were used to relate the physicochemical properties of the polymers and fibers … Simulated adsorption isotherms that describe the irreversible binding of cationic polydisperse polymers onto anionic porous wood pulp fibers were used to relate the physicochemical properties of the polymers and fibers to five attributes of both simulated and experimental isotherms. The analysis is complicated because the lower molecular weight fractions of the adsorbing polymer access more fiber surface area compared to the larger chains. A key assumption is that Γ = λ·ssa = CP·D, where Γ (mg/g) is the amount of adsorbed polymer, λ (mg/m2) is the coverage, ssa (m2/g) is the accessible specific surface area, CP is the cumulative polymer chain length probability, and D is the corresponding polymer dose. The polymers are assumed to have a log-normal chain length distribution characterized by a mean, nm, and a coefficient of variation, cv. The final polymer property is the Mark-Houwink exponent β. The fiber's accessible specific surface area, ssa, was assumed to be a power-law function of the adsorbing polymer chain length. This power law is described by three properties: the slope, the ssa of the exterior fiber surfaces, and the corresponding polymer chain length. Simulated isotherms exhibited the general features of published isotherms. The simulations indicated the links between five isotherm attributes and six simulated isotherm physical properties. Comparisons with published adsorption data supported this approach.
Abstract Adhesion to wet surfaces and other harsh environments is of significant importance in various fields. However, developing instant and strong underwater adhesives for long‐term use still remains highly challenging. … Abstract Adhesion to wet surfaces and other harsh environments is of significant importance in various fields. However, developing instant and strong underwater adhesives for long‐term use still remains highly challenging. Herein, a novel adhesive (PUU‐FPD) that incorporates bulky hydrophobic “tentacles” and hydrophilic “anchors” within the network is reported inspired by the structure of barnacle cement proteins. The hydrophobic side chains can effectively remove bound water from the substrate surface through hydrophobic self‐assembly. Due to the hindrance of hydrophobic branches, the hydrophilic free urea/urethane groups in the protection area provide abundant hydrogen bonding bridges on the adhered surfaces, achieving instant and robust adhesion on various substrates (poly(methyl methacrylate), ceramic, steel, glass, polytetrafluoroethylene, and wood). The adhesive strength increases over time and reaches the maximum value (1.62 MPa) at ≈24 h. Remarkably, PUU‐FPD achieves stable adhesion under universal conditions, including extremely low temperatures (−196 °C), underwater, in salt water (35% NaCl solution), and in strong acid or alkaline environments (pH = 1 or 14). Based on dynamic hydrogen bonds, debonding‐rebonding of the adhesive can be recycled multiple times underwater. This underwater adhesive with excellent comprehensive performance offers an alternative material for practical applications, such as underwater sealants, electronic encapsulation, underwater devices, and repair.
Preventing biofouling and bacterial infections are pivotal issues in developing implantable biomaterials. Zwitterionic hydrogels stand out for their antifouling effects and high biocompatibility, making them ideal for biomedical applications. However, … Preventing biofouling and bacterial infections are pivotal issues in developing implantable biomaterials. Zwitterionic hydrogels stand out for their antifouling effects and high biocompatibility, making them ideal for biomedical applications. However, the lack of direct bactericidal activity and the limited applicability to various materials are key challenges to be addressed in these hydrogel coatings. To address this, a dual-functional hydrogel coating with synergetic antifouling and biocidal properties is proposed to prevent the initial infection and consequent biofilm formation, which can be applied to various types of substrates. This coating is fabricated via photo-crosslinking, combining representative zwitterionic polymer, poly (sulfobetaine methacrylate) (pSBMA), with a cationic bactericidal polymer, poly (2-aminoethyl methacrylate) (pAEMA). Owing to antifouling and contact-killing properties, the p(SBMA-co-AEMA) hydrogel-coated surface can repel non-specific proteins and eradicate bacteria such as E. coli and S. aureus that overcame the antifouling barrier. These results also demonstrate that this hydrogel coating exhibits excellent biocompatibility and can be applied to various substrate materials from polymers to metals. The coating method developed in this study holds great potential for enhancing the performance and safety of various implantable biomaterials and medical devices.
Abstract Biosensors have become integrated into our lives. Current technology requires biosensors not only to have high sensitivity but also to have high specificity for one target, while repelling all … Abstract Biosensors have become integrated into our lives. Current technology requires biosensors not only to have high sensitivity but also to have high specificity for one target, while repelling all other molecules and materials in the biological medium. These goals are met by surfaces that combine a biorecognition element and a high‐quality antifouling layer. In this review, we largely focus on polymer brushes that are grafted from the surface, as these are known to exhibit excellent antifouling properties. We also discuss how to functionalize these with biorecognition elements. Based on the current research on antifouling brushes, we recommend using poly(2‐hydroxypropylmethacrylamide) (HPMAA) and/or poly(carboxybetainemethacrylamide) (CBMAA) brushes, with a thickness between 20–30 nm. Furthermore, we note the importance of high polymer chain densities in such brushes and highlight that a proper comparison requires, among others, similar pre‐treatments. These antifouling brushes are biospecific after receptors are integrated with efficient coupling strategies. Here the opportunities and limitations of frequently used approaches of antifouling polymer brushes within biosensors are highlighted. Also, with the resulting combination of high specificity and low (bio‐)chemical noise levels, we envision an increase in the incorporation of novel polymer brushes for the development of stable biospecific sensors.
Tissue adhesives are increasingly sought after for their potential to minimize invasiveness, simplify surgical procedures, and reduce operative times; however, conventional polyacrylamide (PAM)-based hydrogels are often hindered by irreversible bonding, … Tissue adhesives are increasingly sought after for their potential to minimize invasiveness, simplify surgical procedures, and reduce operative times; however, conventional polyacrylamide (PAM)-based hydrogels are often hindered by irreversible bonding, which limits their reusability and compromises both mechanical integrity and self-healing ability. Motivated by the natural adhesion mechanisms of mussels, we have developed an innovative tissue adhesive hydrogel by incorporating polydopamine (PDA) and cysteine (Cys) into a PAM matrix via free radical polymerization, with polyethylene glycol diacrylate (PEGDA) serving as an effective cross-linker. In our system, PDA contributes essential catechol groups for strong tissue adhesion, while Cys not only preserves these groups from oxidation but also enhances hydrophilic interactions, resulting in a PDA-Cys-PAM hydrogel with a tensile strength of 23.4-30.7 kPa, a fracture elongation of 628-706%, and an elongation recovery of 48%. Significantly, the seamless integration of nanoclay into the hydrogel network further reinforces its structure and improves energy dissipation, leading to a marked enhancement of the self-healing performance─evidenced by an increase in the elongation recovery rate to 71.9%─without compromising the inherent mechanical properties. Moreover, in vitro assays with NIH3T3 cells demonstrate excellent biocompatibility, underscoring the potential of this synergistic design. Overall, our work not only elucidates the distinct and cooperative roles of PDA, Cys, and nanoclay but also represents a significant advancement in the design of reusable, high-performance tissue adhesives for potential applications in tissue repair and regeneration.
This study aims to develop a robust and reproducible method for fabricating efficient ultrathin antifouling coatings on gold surfaces by leveraging hydroxylation-based surface modifications. An ultrathin antifouling coating of a … This study aims to develop a robust and reproducible method for fabricating efficient ultrathin antifouling coatings on gold surfaces by leveraging hydroxylation-based surface modifications. An ultrathin antifouling coating of a monoethylene glycol silane derivative, known to reduce fouling by at least 90% on flat hydroxylated surfaces, was successfully replicated on flat gold (reducing fouling by ~75%) by hydroxylating its surface with β-mercaptoethanol. This tandem coating contains the monoethylene glycol silane layer on top of the β-mercaptoethanol on the gold. Characterization was performed using contact angle goniometry, atomic force microscopy, x-ray photoelectron spectroscopy, and antifouling measurements. The results from these techniques, consistent with the literature, confirmed the successful and reproducible application of the tandem coating. Through heterogeneities, including defects and incomplete coverage, the AFM data revealed distinct visible layers of the tandem coating. The direct application of monoethylene glycol silane onto gold resulted in superior antifouling performance (88% reduction), demonstrating that direct silylation exploits pre-existing oxygen-containing species on the gold surface for a more effective antifouling layer. These findings offer a scalable approach for engineering antifouling coatings on gold substrates, with potential applications in biosensing and implantable device antifouling technologies.
When the topology of polymer brushes is changed from linear to cyclic or looped, many of the brush properties will be improved. Yet, whether such a topology variation also affects … When the topology of polymer brushes is changed from linear to cyclic or looped, many of the brush properties will be improved. Yet, whether such a topology variation also affects the (vapor-)solvation and swelling of brushes has remained unclear. In fact, in a recent publication, Vagias and co-workers (Macromolecular Rapid Communications 2023, 44 (9), 2300035) reported an unequal swelling for linear and cyclic brushes and challenged theoreticians to develop a new Flory-Huggins theory that includes topology effects. In this letter, we address this challenge and employ molecular dynamics simulations to study the vapor swelling of linear, looped, and cyclic brushes. We find that the emergence of equal or unequal swelling for different topologies depends on the definition of the grafting density that is kept constant in the comparison. When suitably defined, the degree of swelling is independent of the topology, and the Flory-Huggins theory for brushes will describe brush swelling for all topologies in the present study.