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Antifouling coatings are vital to enhance the performance of medical devices, aiming to mitigate bodily reactions by shielding their surface. Despite significant advancements in antifouling coatings, like those based on zwitterionic monomers and hydroxyl-functionalized (meth)acrylamides, limitations like decreased antifouling properties after functionalization and complement system activation hinder their application in blood. Here, a novel class of ultrathin surface-attached hydrogels is presented, consisting of hydrophilic non-charged green solvent-based monomers and preventing protein adsorption while offering on-demand degradability. Unlike the best antifouling brushes, the coatings are easily applicable, unaffected by charges, and free of complement system-activating groups. The hydrogels are formed using copolymers of N,N-dimethyl lactamide acrylate (DMLA) and benzophenone acrylate (BPA). Moreover, 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) is incorporated to introduce hydrolyzable ester. The coating of state-of-the-art devices is demonstrated with X-ray photoelectron spectroscopy (XPS), analyze surface energy components, and confirm their antifouling properties with surface plasmon resonance (SPR). The coatings are non-cytotoxic toward MRC-5 fibroblasts, exhibit repellency against methicillin-resistant Staphylococcus aureus (MRSA), and effectively prevent thrombus formation on devices in blood. This work establishes a versatile platform for next-generation coatings in medical and industrial applications, matching the antifouling efficiency of the most advanced solutions and offering regeneration of substrates by erasing the coating.

JTD

Arborescent (dendrigraft) polymers are high-molecular-weight dendritic macromolecules with a regular, multilevel branched topology and a high density of functional end groups in their periphery. Their well-defined architecture, devoid of cross-links or loops, imparts a particle-macromolecule duality that becomes particularly pronounced at interfaces. However, the underlying mechanisms governing their interfacial behavior remain largely unexplored. Here, we elucidate how the unique topology dictates the interfacial organization of water-soluble arborescent polymers. Using an iterative grafting-from approach via single-electron transfer living radical polymerization, we synthesized narrowly dispersed polymers with controlled branching and ultra-high molecular weight of 6.2 x 106 g mol-1. These polymers transition from spherical rigid particles in solution, to highly flexible, two-dimensional conformations upon interfacial adsorption. At solid interfaces, increasing segment density shifts surface morphologies from quasi-2D discs to fried-egg-like structures, as observed by atomic force microscopy and corroborated by dissipative particle dynamics simulations. At liquid-liquid interfaces, the absence of substrate constraints facilitates complete spreading into uniform 2D discs, driven by the energy gain due to polymer-segment adsorption. Furthermore, we uncover that macromolecular crowding and topological constraints inherent to the arborescent architecture dictate the response to compression of the adsorbed polymer layer, contrasting sharply with the behavior of conventional flexible linear or star polymers. The combination of high interfacial activity, spatially adaptable end groups, and extreme molecular flexibility will enable arborescent polymers to adapt to complex interfaces, acting as versatile platforms for multivalent and superselective interactions. These properties open new avenues for designing multivalent nanocarriers and adaptive interfacial materials with cooperative binding effects.

JTD Keywords: Angle neutron-scattering, Architectur, Graft, Microgels, Polymers, Polystyrene-graft-poly(2-vinylpyridine) copolymers, Polystyrenes, Radical polymerization, Set, Unimolecular micelles

Cell membranes play a key role in bottom-up synthetic biology, as they enable interaction control, transport, and other essential functions. These ultra-thin, flexible, yet stable structures form through the self-assembly of lipids and proteins. While liposomes are common mimics, their synthetic membranes often fail to replicate natural properties due to poor structural control. To address this, pepticombs are introduced, a new family of supramolecular building blocks. They are synthesized by regularly appending anionic surfactants with lipid-long alkyl tails to cationic amino acid residues of recombinant elastin-like supercharged unfolded polypeptides (SUPs). Using microscopy techniques and molecular dynamics simulations, the formation of giant unilamellar vesicles, termed pepticombisomes, is demonstrated and their membrane properties are characterized. The molecular topology of pepticombs allows for precise mimicry of membrane thickness and flexibility, beyond classic polymersomes. Unlike the previously introduced ionically-linked comb polymers, all pepticombs exhibit a uniform degree of polymerization, composition, sequence, and spontaneous curvature. This uniformity ensures consistent hydrophobic tail distribution, facilitating intermolecular hydrogen bonding within the backbone. This generates elastic heterogeneities and the concomitant formation of non-icosahedral faceted vesicles, as previously predicted. Additionally, pepticombisomes can incorporate functional lipids, enhancing design flexibility.

JTD Keywords: Biomimetic synthesis, Bottom-up synthetic biology, Cholesterol, Dynamics, Glycodendrimersomes, Janus dendrimers, Lipids, Nanoscal, Organization, Polymersome membranes, Protein, Stability, Supercharged peptides, Synthetic cells, Vesicle

The global dental implant market is projected to reach $9.5 billion by 2032, growing at a 6.5% compound annual growth rate due to the rising prevalence of dental diseases. Importantly, this growth raises concerns about postoperative infections, which present significant challenges within our healthcare system and lead to a two-thirds failure rate for infected implants. In this study, we present an innovative multilevel coating system that makes the surface of dental titanium implants resistant to bacterial colonization, thereby minimizing the risk of infection development. This multilevel coating features a nanometer-thick biohybrid coating layer combined with a microgroove surface microstructuring, creating physical barriers that enhance the stability of the biohybrids against mechanical abrasion. Our coating demonstrates excellent biocompatibility and strong antifouling properties against undiluted blood plasma proteins. Furthermore, the combination of surface microstructuring and the biohybrid coating remains stable under prolonged mechanical stress simulation and effectively repels clinically relevant bacteria, achieving a 99% reduction in bacterial colonization on the implant. These findings underscore the potential of this approach to prevent implant-associated infections and highlight the critical role of surface engineering in ensuring long-term implant performance.

JTD Keywords: Antifouling, Bacteriarepellency, Biofilm formatio, Dental titanium implants, Infection preventio, Protein-polymer biohybrids, Ti-binding peptide, Usp laser microstructuring

Blood-contacting medical devices, especially extracorporeal membrane oxygenators (ECMOs), are highly susceptible to surface-induced coagulation because of their extensive surface area. This can compromise device functionality and lead to life-threatening complications. High doses of anticoagulants, combined with anti-thrombogenic surface coatings, are typically employed to mitigate this risk, but such treatment can lead to hemorrhagic complications. Therefore, bioactive surface coatings that mimic endothelial blood regulation are needed. However, evaluating these coatings under realistic ECMO conditions is both expensive and challenging. This study utilizes microchannel devices to simulate ECMO fluid dynamics and assess the clot-lysis efficacy of a self-activating fibrinolytic coating system. The system uses antifouling polymer brushes combined with tissue plasminogen activator (tPA) to induce fibrinolysis at the surface. Here, tPA catalyzes the conversion of blood plasminogen into plasmin, which dissolves clots. This positive feedback loop enhances clot digestion under ECMO-like conditions. This findings demonstrate that this coating system can significantly improve the hemocompatibility of medical device surfaces.

JTD

Surface plasmon resonance (SPR) is a key technique in developing sensor platforms for clinical diagnostics, drug discovery, food quality, and environmental monitoring applications. While prism-coupled (Kretschmann) SPR remains a "gold-standard" for laboratory work-flows due to easier fabrication, handling and high through put, other configurations such as grating-coupled SPR (GC-SPR) and wave-guide mode SPR are yet to fulfil their technology potential. This work evaluates the technical aspects influencing the performance of GC-SPR and reviews recent progress in the fabrication of such platforms. In principle, the GC-SPR involves the illumination of the plasmonic metal film with periodic gratings to excite the surface plasmons (SP) via diffraction-based phase matching. The real performance of the GC-SPR is, however, heavily influenced by the topography of the grating structures produced via top-down lithography techniques. This review discusses latest in approaches to achieve consistent plasmonic gratings with uniform features and periodicity over a large scale and explores the choice of plasmon-active and substrate material for enhanced performance. The review also provides insights into the different GC-SPR measurement configurations and highlights on opportunities with their potential applications as biosensors with translational capabilities. A review on recent progress in the realization of grating-coupled and wave-guide mode surface plasmon resonance (SPR) platforms which have seen very limited progress toward diagnostics applications in comparison to Kretchmann configured SPR. Sophisticated topography manipulation during large-area nanofabrication, integration of emerging nanomaterials, and machine learning-based data analytics are expected to overcome concurrent challenges toward clinical adoption of grating-coupled SPR in coming years. image

JTD Keywords: Aluminum, Biosensor, Chemical sensor, Compact, Fabrication methods, Gc-spr, Gold, Lase, Lithography, Nanogratings, Performance, Plasmonics, Sensitivity enhancement, Sp, Spr sensor

Biomaterial-associated infections (BAIs) pose significant challenges in modern medical technologies, being a major postoperative complication and leading cause of implant failure. These infections significantly risk patient health, resulting in prolonged hospitalization, increased morbidity and mortality rates, and elevated treatment expenses. This comprehensive review examines the mechanisms driving bacterial adhesion and biofilm formation on biomaterial surfaces, offering an in-depth analysis of current antimicrobial strategies for preventing BAIs. We explore antimicrobial-eluting biomaterials, contact-killing surfaces, and antifouling coatings, emphasizing the application of antifouling polymer brushes on medical devices. Recent advancements in multifunctional antimicrobial biomaterials, which integrate multiple mechanisms for superior protection against BAIs, are also discussed. By evaluating the advantages and limitations of these strategies, this review aims to guide the design and development of highly efficient and biocompatible antimicrobial biomaterials. We highlight potential design routes that facilitate the transition from laboratory research to clinical applications. Additionally, we provide insights into the potential of synthetic biology as a novel approach to combat antimicrobial resistance. This review aspires to inspire future research and innovation, ultimately improving patient outcomes and advancing medical device technology.

JTD Keywords: Animals, Anti-bacterial agents, Antifouling coatings, Antimicrobial peptide, Antimicrobial-eluting coatings, Antimicrobial‐eluting coatings, Bacterial adhesion, Bacterial biofilm formation, Biocompatible materials, Biofilms, Biomaterial-associated infections, Biomaterial‐associated infections, Contact killing coatings, Humans, In-vitr, Infused porous surfaces, Metal-oxide surfaces, Multifunctional antimicrobial coating, Multifunctional antimicrobial coatings, Poly(l-lysine)-g-poly(ethylene glycol) layers, Polymer brushes, Prosthesis-related infections, Silicone oil, Superhydrophobic surfaces, Urinary catheters

Endothelium, the lining in this blood vessel, orchestrates three main critical functions such as protecting blood components, modulating of hemostasis by secreting various inhibitors, and directing clot digestion (fibrinolysis) by activating tissue plasminogen activator. No other surface can perform these tasks; thus, the contact of blood and blood-contacting medical devices inevitably leads to the activation of coagulation, often causing device failure, and thromboembolic complications. This perspective, first, discusses the biological mechanisms of activation of coagulation and highlights the efforts of advanced coatings to recapitulate one characteristic of endothelium, hereafter single functions of endothelium and noting necessity of the synergistic integration of its three main functions. Subsequently, it is emphasized that to overcome the challenges of blood compatibility an endothelium-mimicking system is needed, proposing a synergy of bottom-up synthetic biology, particularly synthetic cells, with passive- and bioactive surface coatings. Such integration holds promise for developing advanced biomaterials capable of recapitulating endothelial functions, thereby enhancing the hemocompatibility and performance of blood-contacting medical devices. The activation of coagulation on the surface of blood-contacting medical devices often leads to thromboembolic complications. A concept for the next generation of hemocompatbile surfaces inspired by endothelium is proposed. This concept not only contribute to the fundamental understanding of hemocompatibility but also offer practical implications for the design and development of biomedical devices with enhanced biocompatibility and functionality. image

JTD Keywords: Animals, Antifouling coatings, Antifouling polymer brushes, Biocompatible materials, Blood coagulation, Coagulation-factor-xii, Coated materials, biocompatible, Endothelium, Endothelium, vascular, Endothelium-inspired, Endothelium‐inspired, Hemocompatibility, Hemocompatible surface coatings, Hemostasis, Heparin-induced thrombocytopenia, Humans, Nitric-oxide release, Of-the-art, Peptide macrocycle inhibitor, Plasma contact system, Protein-adsorption, Self-assembled monolayers, Surface modificatio, Synthetic endotheliu, Synthetic endothelium

Orthopedic implants such as knee and hip implants are one of the most important types of medical devices. Currently, the surface of the most advanced implants consists of titanium or titanium-alloys with high porosity at the bone-contacting surface leading to superior mechanical properties, excellent biocompatibility, and the capability of inducing osseointegration. However, the increased surface area of porous titanium provides a nidus for bacteria colonization leading to implant-related infections, one of the main reasons for implant failure. Here, two readily applicable titanium-coatings based on hydrophilic carboxybetaine polymers that turn the surface stealth thereby preventing bacterial adhesion and colonization are developed. These coatings are biocompatible, do not affect cell functionality, exhibit great antifouling properties, and do not cause additional inflammation during the healing process. In this way, the coatings can prevent implant-related infections, while at the same time being completely innocuous to its biological environment. Thus, these coating strategies are a promising route to enhance the biocompatibility of orthopedic implants and have a high potential for clinical use, while being easy to implement in the implant manufacturing process.© 2023 The Authors. Macromolecular Bioscience published by Wiley-VCH GmbH.

JTD Keywords: bacteria repellency, biocompatibility, blood-plasma, brushes, stealth coatings, surface, titanium implants, Antifouling surfaces, Bacteria repellency, Biocompatibility, Brushes, Polymer brushes, Stealth coatings, Titanium implants

Factor XII (FXII) is a zymogen present in blood that tends to adsorb onto the surfaces of blood-contacting medical devices. Once adsorbed, it becomes activated, initiating a cascade of enzymatic reactions that lead to surface-induced coagulation. This process is characterized by multiple redundancies, making it extremely challenging to prevent clot formation and preserve the properties of the surface. In this study, a novel modulatory coating system based on C1-esterase inhibitor (C1INH) functionalized polymer brushes, which effectively regulates the activation of FXII is proposed. Using surface plasmon resonance it is demonstrated that this coating system effectively repels blood plasma proteins, including FXII, while exhibiting high activity against activated FXII and plasma kallikrein under physiological conditions. This unique property enables the modulation of FXII activation without interfering with the overall hemostasis process. Furthermore, through dynamic Chandler loop studies, it is shown that this coating significantly improves the hemocompatibility of polymeric surfaces commonly used in medical devices. By addressing the root cause of contact activation, the synergistic interplay between the antifouling polymer brushes and the modulatory C1INH is expected to lay the foundation to enhance the hemocompatibility of medical device surfaces.© 2023 The Authors. Macromolecular Bioscience published by Wiley-VCH GmbH.

JTD Keywords: adsorption, binding, c1-esterase-inhibitor, coatings, contact activation, factor-xii, fxii activation, hemocompatibility, hemocompatible surface modification, heparin, polymer brushes, system, thrombosis, Adsorption, Anticoagulation, Antifouling agent, Article, Beta-fxiia, Biocompatibility, Blood, Blood clotting, Blood clotting factor 12, Blood clotting factor 12a, Blood clotting factor 12a inhibitor, Blood coagulation, C1-esterase-inhibitor, Cell activation, Chemical activation, Coagulation, Coating (procedure), Complement component c1s inhibitor, Complement system, Controlled study, Dendrimers, Enzyme immobilization, Enzymes, Erythrocyte, Esters, Factor xii, Factor xii activation, Factor xiia, Fibrin deposition, Functional polymers, Fxii activation, Haemocompatibility, Hemocompatibility, Hemocompatible surface modification, Hemostasis, Heparin, Human, Hydrogel, Medical devices, Metabolism, Plasma kallikrein, Plasma protein, Plastic coatings, Platelet count, Polymer, Polymer brushes, Polymerization, Polymers, Property, Root cause, Surface plasmon resonance, Surface property, Surface reactions, Surface-modification, Thrombocyte adhesion, Β-fxiia

The accurate spatial segregation into distinct phases within cell membranes coordinates vital biochemical processes and functionalities in living organisms. One of nature's strategies to localize reactivity is the formation of dynamic raft domains. Most raft models rely on liquid-ordered L-0 phases in a liquid-disordered L-d phase lacking correlation and remaining static, often necessitating external agents for phase separation. Here, we introduce a synthetic system of bicomponent glycodendrimersomes coassembled from Janus dendrimers and Janus glycodendrimers (JGDs), where lactose-lactose interactions exclusively drive lateral organization. This mechanism results in modulated phases across two length scales, yielding raft-like microdomains featuring nanoarrays at the nanoscale. By varying the density of lactose and molecular architecture of JGDs, the nanoarray type and size, shape, and spacing of the domains were controlled. Our findings offer insight into the potential primordial origins of rudimentary raft domains and highlight the crucial role of glycans within the glycocalyx.

JTD Keywords: Article, Artificial cells, Atomic force microscopy, Bicomponents, Bilayer, Bilayer membrane, Biochemical functionality, Biochemical process, Biological-membranes, Cell component, Cell membrane, Cellular parameters, Chemical interaction, Chemical structure, Chemistry, Cytology, Defined janus glycodendrimers, Dehydration, Dendrimer, Dendrimers, Dilution, Dimer, External agents, Fourier transform, Giant vesicles, Glycan, Glycans, Glycocalyx, Glycodendrimers, Janus dendrimer, Janus glycodendrimer, Lactose, Lateral organization, Lectin, Lipid rafts, Living organisms, Membrane damage, Membrane microdomain, Membrane microdomains, Membrane structure, Metabolism, Modulated phases, Molecule, Monomer, Nanoarrays, Oligosaccharide, Organization, Periodicity, Phase separation, Phase-separation, Phospholipids, Polysaccharide, Polysaccharides, Raft like domain, Relative humidity, Spatial segregation, Structure analysis, Sugars, Synthetic systems, Tetramer, Unclassified drug, Unilamellar vesicles, Water

Medical devices are crucial for patient care, yet even the best biomaterials lead to infections and unwanted activation of blood coagulation, potentially being life-threatening. While hydrophilic polymer brushes are the best coatings to mitigate these issues, their reliance on fossil raw materials underscores the urgency of bio-based alternatives. In this work, we introduce polymer brushes of a green solvent-based monomer, prohibiting protein adsorption, bacterial colonization, and blood clot formation at the same level as fossil-based polymer brushes. The polymer brushes are composed of N,N-dimethyl lactamide acrylate (DMLA), can be polymerized in a controlled manner, and show strong hydrophilicity as determined by thermodynamic analysis of the surface tension components. The contact of various challenging protein solutions results in repellency on the poly(DMLA) brushes. Furthermore, the poly(DMLA) brushes completely prevent the adhesion and colonization of Escherichia coli. Remarkably, upon blood contact, the poly(DMLA) brushes successfully prevent the formation of a fibrin network and leukocyte adhesion on the surface. While showcasing excellent antifouling properties similar to those of N-hydroxypropyl methacrylamide (HPMA) polymer brushes as one of the best antifouling coatings, the absence of hydroxyl groups prevents activation of the complement system in blood. We envision the polymer brushes to contribute to the future of hemocompatible coatings.

JTD Keywords: blood-plasma, coatings, contact, fossil, poly(2-methacryloyloxyethyl phosphorylcholine), protein adsorption, resistance, self-assembled monolayers, sulfobetaine, Surface-energy components

The immobilization of vesicles has been conceptualized as a method to functionalize biointerfaces. However, the preservation of their integrity post immobilization remains a considerable challenge. Interfacial interactions can cause vesicle rupture upon close surface contact and non-specific protein adsorption impairing surface functions. To date, immobilization of vesicles has relied solely on either entrapment or prior modification of vesicles, both of which require laborious preparation and limit their applications. This work develops a bioinspired strategy to pin vesicles without prior modification while preserving their intact shape. This work introduces antifouling diblock copolymers and ultrathin surface-attached hydrogels containing a brush-like interface consisting of a bottle brush copolymer of N-(2-hydroxypropyl) methacrylamide (HPMA) and N-(3-methacrylamidopropyl)-N,N-dimethyldodecan-1-aminiumiodide (C12+). The presence of positive charges generates an attractive force that pulls vesicles toward the surface. At the surface, the amphiphilic properties of the combs facilitate their insertion into the membrane, mimicking the harpooning mechanism observed in antimicrobial peptides. Importantly, the antifouling poly(HPMA) backdrop serves to safeguard the vesicles by preventing deformation and breakage. Using a combination of thermodynamic analysis, surface plasmon resonance, and confocal laser scanning microscopy, this work demonstrates the efficiency of this biomimetic system to capture vesicles while maintaining an antifouling interface necessary for bioapplications. This work presents a novel supramolecular approach that combines three key elements: long-range attraction, vesicle pinning, and short-range repulsion to attract and harpoon vesicles, while protecting them at the surface. This work envisions these coatings as universal and biocompatible platforms that can be used not only to study vesicle interactions, but also as tools for biomedical applications.image

JTD Keywords: Antifouling coatings, Coatings, Delivery, Extracellular vesicles, Fabrication, Hydrogel, Janus dendrimers, Lipid vesicles, Liposomes, Membrane insertion, Polymer brushes, Proteins, Surface-energy components, Ultrathin surface-attached hydrogels, Vesicle pinning

Building functional mimics of cell membranes is an important task toward the development of synthetic cells. So far, lipid and amphiphilic block copolymers are the most widely used amphiphiles with the bilayers by the former lacking stability while membranes by the latter are typically characterized by very slow dynamics. Herein, we introduce a new type of Janus dendrimer containing a zwitterionic phosphocholine hydrophilic headgroup (JDPC ) and a 3,5-substituted dihydrobenzoate-based hydrophobic dendron. JDPC self-assembles in water into zwitterionic dendrimersomes (z-DSs) that faithfully recapitulate the cell membrane in thickness, flexibility, and fluidity, while being resilient to harsh conditions and displaying faster pore closing dynamics in the event of membrane rupture. This enables the fabrication of hybrid DSs with components of natural membranes, including pore-forming peptides, structure-directing lipids, and glycans to create raft-like domains or onion vesicles. Moreover, z-DSs can be used to create active synthetic cells with life-like features that mimic vesicle fusion and motility as well as environmental sensing. Despite their fully synthetic nature, z-DSs are minimal cell mimics that can integrate and interact with living matter with the programmability to imitate life-like features and beyond. This article is protected by copyright. All rights reserved.This article is protected by copyright. All rights reserved.

JTD Keywords: biological-membranes, bottom-up synthetic biology, chain, hybrid vesicles, hydroethidine, organization, polymersome, proteins, stability, synthetic cells, thickness, vesicle fusion, vesicle motility, vesicles, zwitterionic dendrimersomes, Biosensor, Biosensors, Bottom-up synthetic biology, Hybrid vesicles, Lipid-bilayers, Synthetic cells, Vesicle fusion, Vesicle motility, Zwitterionic dendrimersomes

JTD Keywords: Life below water

JTD Keywords: anti-fxiia antibody, artificial surfaces, blood compatibility, complement activation, factor xii, fibrinolytic system, hemocompatible coatings, interactive hemocompatibility, poly(2-methacryloyloxyethyl phosphorylcholine), polyethylene oxide, polymer brushes, radical polymerization, sequential coimmobilization, Antifouling polymer brushes, Protein adsorption

Whenever an artificial surface comes into contact with blood, proteins are rapidly adsorbed onto its surface. This phenomenon, termed fouling, is then followed by a series of undesired reactions involving activation of complement or the coagulation cascade and adhesion of leukocytes and platelets leading to thrombus formation. Thus, considerable efforts are directed towards the preparation of fouling-resistant surfaces with the best possible hemocompatibility. Herein, a comprehensive hemocompatibility study after heparinized blood contact with seven polymer brushes prepared by surface-initiated atom transfer radical polymerization is reported. The resistance to fouling is quantified and thrombus formation and deposition of blood cellular components on the coatings are analyzed. Moreover, identification of the remaining adsorbed proteins is performed via mass spectroscopy to elucidate their influence on the surface hemocompatibility. Compared with an unmodified glass surface, the grafting of polymer brushes minimizes the adhesion of platelets and leukocytes and prevents the thrombus formation. The fouling from undiluted blood plasma is reduced by up to 99%. Most of the identified proteins are connected with the initial events of foreign body reaction towards biomaterial (coagulation cascade proteins, complement component, and inflammatory proteins). In addition, several proteins that are not previously linked with blood-biomaterial interaction are presented and discussed.

JTD Keywords: antifouling surfaces, biosensor, blood-plasma, coagulation, coatings, compatibility, glycoprotein, hemocompatibility, identification, methacrylate), ms identification, polymer brushes, protein adsorption, surface-chemistry, Antifouling surfaces, High-density-lipoprotein, Protein adsorption

We report a green solvent-to-polymer upgrading transformation of chemicals of the lactic acid portfolio into water-soluble lower critical solution temperature (LCST)-type acrylic polymers. Aqueous Cu(0)-mediated living radical polymerization (SET-LRP) was utilized for the rapid synthesis of N-substituted lactamide-type homo and random acrylic copolymers under mild conditions. A particularly unique aspect of this work is that the water-soluble monomers and the SET-LRP initiator used to produce the corresponding polymers were synthesized from biorenewable and non-toxic solvents, namely natural ethyl lactate and BASF's Agnique (R) AMD 3L (N,N-dimethyl lactamide, DML). The pre-disproportionation of Cu(I) Br in the presence of tris[2-(dimethylamino)ethyl]amine (Me6TREN) in water generated nascent Cu(0) and Cu(II) complexes that facilitated the fast polymerization of N-tetrahydrofurfuryl lactamide and N,N-dimethyl lactamide acrylate monomers (THFLA and DMLA, respectively) up to near-quantitative conversion with excellent control over molecular weight (5000 < M-n < 83 000) and dispersity (1.05 < D < 1.16). Interestingly, poly(THFLA) showed a degree of polymerization and concentration dependent LCST behavior, which can be fine-tuned (T-cp = 12-62 degrees C) through random copolymerization with the more hydrophilic DMLA monomer. Finally, covalent cross-linking of these polymers resulted in a new family of thermo-responsive hydrogels with excellent biocompatibility and tunable swelling and LCST transition. These illustrate the versatility of these neoteric green polymers in the preparation of smart and biocompatible soft materials.

JTD Keywords: Acid, Ethyl lactate, Living radical polymerization, Monomers, Pnipam, Reductive amination, Ruthenium nanoparticles, Set-lrp, Single, Thermoresponsive polymers

The integration of active cell machinery with synthetic building blocks is the bridge toward developing synthetic cells with biological functions and beyond. Self-replication is one of the most important tasks of living systems, and various complex machineries exist to execute it. In Escherichia coli, a contractile division ring is positioned to mid-cell by concentration oscillations of self-organizing proteins (MinCDE), where it severs membrane and cell wall. So far, the reconstitution of any cell division machinery has exclusively been tied to liposomes. Here, the reconstitution of a rudimentary bacterial divisome in fully synthetic bicomponent dendrimersomes is shown. By tuning the membrane composition, the interaction of biological machinery with synthetic membranes can be tailored to reproduce its dynamic behavior. This constitutes an important breakthrough in the assembly of synthetic cells with biological elements, as tuning of membrane-divisome interactions is the key to engineering emergent biological behavior from the bottom-up.

JTD Keywords: bacterial cell division, bottom-up synthetic biology, dendrimersomes, dynamic min patterns, ftsz assembly, Artificial cells, Bacterial cell division, Bacterial proteins, Bottom-up synthetic biology, Cell division, Cell wall, Dendrimersomes, Dynamic min patterns, Dynamics, Escherichia coli, Escherichia coli proteins, Ftsz assembly, Ftsz filaments, Mind, Organization, Pole oscillation, Polymersome membranes, Proteins, Rapid pole, Synthetic cells, Vesicles

JTD Keywords: biosensor, blood-plasma, chemistry, coatings, design, microchannel cantilever spotting, strain-promoted alkyne-azide cycloaddition, ultra-low fouling hierarchical polymer brushes, Alkyne cycloaddition, Coupling efficiency

The construction of biomembranes that faithfully capture the properties and dynamic functions of cell membranes remains a challenge in the development of synthetic cells and their application. Here a new concept for synthetic cell membranes based on the self-assembly of amphiphilic comb polymers into vesicles, termed ionic combisomes (i-combisomes) is introduced. These combs consist of a polyzwitterionic backbone to which hydrophobic tails are linked by electrostatic interactions. Using a range of microscopies and molecular simulations, the self-assembly of a library of combs in water is screened. It is discovered that the hydrophobic tails form the membrane's core and force the backbone into a rod conformation with nematic-like ordering confined to the interface with water. This particular organization resulted in membranes that combine the stability of classic polymersomes with the biomimetic thickness, flexibility, and lateral mobility of liposomes. Such unparalleled matching of biophysical properties and the ability to locally reconfigure the molecular topology of its constituents enable the harboring of functional components of natural membranes and fusion with living bacteria to “hijack” their periphery. This provides an almost inexhaustible palette to design the chemical and biological makeup of the i-combisomes membrane resulting in a powerful platform for fundamental studies and technological applications.

JTD Keywords: amphiphilic comb polymers, bottom-up synthetic biology, hybrid vesicles, polyelectrolyte-surfactant complexes, polymersomes, synthetic biomembranes, Amphiphilic comb polymers, Biomimetics, Bottom-up synthetic biology, Hybrid vesicles, Hydrophobic and hydrophilic interactions, Liposomes, Polyelectrolyte-surfactant complexes, Polymers, Polymersomes, Synthetic biomembranes, Vesicle fusion, Water