"Dissolve-on-Demand" 3D Printed Materials: Polymerizable Eutectics for Generating High Modulus, Thermoresponsive and Photoswitchable Eutectogels.

Solvent-free photopolymerization of vinyl monomers to produce high modulus materials with applications in 3D printing and photoswitchable materials is demonstrated. Polymerizable eutectic (PE) mixtures are prepared by simply heating and stirring various molar ratios of N-isopropylacrylamide (NIPAM), acrylamide (AAm) and 2-hydroxyethyl methacrylate (HEMA). The structural and thermal properties of the resulting mixtures are evaluated by 1D and 2D NMR spectroscopy as well as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). UV photocuring kinetics of the PE mixtures are evaluated via in situ photo-DSC and photorheology measurements. The PE mixtures cure rapidly and display storage moduli that are orders of magnitude greater than equivalent copolymers cured in an aqueous medium. The versatility of these PE systems is demonstrated through the addition of a photoswitchable spiropyran acrylate monomer, as well as applying the PE formulation as a stereolithography (SLA)-based 3D printing resin. Due to the hydrogen-bonding network in PE systems, 3D printing of the eutectic resin is possible in the absence of crosslinkers. The addition of a RAFT agent to reduce average polymer chain length enables 3D printing of materials which retain their shape and can be dissolved on demand in appropriate solvents. This article is protected by copyright. All rights reserved.

Mimicking Charged Host-Defense Peptides to Tune the Antifungal Activity and Biocompatibility of Amphiphilic Polymers.

Invasive fungal infections impose a substantial global health burden. They cause more than 1.5 million deaths annually and are insufficiently met by the currently approved antifungal drugs. Antifungal peptides are a promising alternative to existing antifungal drugs; however, they can be challenging to synthesize, and are often susceptible to proteases in vivo. Synthetic polymers which mimic the properties of natural antifungal peptides can circumvent these limitations. In this study, we developed a library of 29 amphiphilic polyacrylamides with different charged units, namely, amines, guanidinium, imidazole, and carboxylic acid groups, representative of the natural amino acids lysine, arginine, histidine, and glutamic acid. Ternary polymers incorporating primary ammonium (lysine-like) or imidazole (histidine-like) groups demonstrated superior activity against Candida albicans and biocompatibility with mammalian cells compared to the polymers containing the other charged groups. Furthermore, a combination of primary ammonium, imidazole, and guanidinium (arginine-like) within the same polymer outperformed the antifungal drug amphotericin B in terms of therapeutic index and exhibited fast C. albicans-killing activity. The most promising polymer compositions showed synergistic effects in combination with caspofungin and fluconazole against C. albicans and additionally demonstrated activity against other clinically relevant fungi. Collectively, these results indicate the strong potential of these easily producible polymers to be used as antifungals.

Effect of Star Topology Versus Linear Polymers on Antifungal Activity and Mammalian Cell Toxicity.

The global increase in invasive fungal infections and the emergence of drug-resistant strains demand the urgent development of novel antifungal drugs. In this context, synthetic polymers with diverse compositions, mimicking natural antimicrobial peptides, have shown promising potential for combating fungal infections. This study investigates how altering polymer end-groups and topology from linear to branched star-like structures affects their efficacy against Candida spp., including clinical isolates. Additionally, the polymers' biocompatibility is accessed with murine embryonic fibroblasts and red blood cells in vitro. Notably, a low-molecular weight star polymer outperforms both its linear polymeric counterparts and amphotericin B (AmpB) in terms of an improved therapeutic index and reduced haemolytic activity, despite a higher minimum inhibitory concentration against Candida albicans (C. albicans) SC5314 (16-32 µg mL-1 vs 1 µg mL-1 for AmpB). These findings demonstrate the potential of synthetic polymers with diverse topologies as promising candidates for antifungal applications.

Polymerization Induced Microphase Separation of ABC Triblock Copolymers for 3D Printing Nanostructured Materials.

Polymerization-induced microphase separation (PIMS) is a versatile technique for producing nanostructured materials. In previous PIMS studies, the predominant approach involved employing homopolymers as macromolecular chain transfer agents (macroCTAs) to mediate the formation of nanostructured materials. In this article, the use of AB diblock copolymers as macroCTAs to design PIMS systems for 3D printing of nanostructured materials is investigated. Specifically, the influence of diblock copolymer composition and block sequence on the resulting nanostructures, and their subsequent impact on bulk properties is systematically investigated. Through careful manipulation of the A/B block ratios, the morphology and size of the nanodomains are successfully controlled. Remarkably, the sequence of A and B blocks significantly affects the microphase separation process, resulting in distinct morphologies. The effect can be attributed to changes in the interaction parameters (χAB , χBC , χAC ) between the different block segments. Furthermore, the block sequence and composition exert profound influence on the thermomechanical, tensile, and swelling properties of 3D printed nanostructured materials. By leveraging this knowledge, it becomes possible to design advanced 3D printable materials with tailored properties, opening new avenues for material engineering.

Customized Nanostructured Ceramics via Microphase Separation 3D Printing.

To date, the restricted capability to fabricate ceramics with independently tailored nano- and macroscopic features has hindered their implementation in a wide range of crucial technological areas, including aeronautics, defense, and microelectronics. In this study, a novel approach that combines self- and digital assembly to create polymer-derived ceramics with highly controlled structures spanning from the nano- to macroscale is introduced. Polymerization-induced microphase separation of a resin during digital light processing generates materials with nanoscale morphologies, with the distinct phases consisting of either a preceramic precursor or a sacrificial polymer. By precisely controlling the molecular weight of the sacrificial polymer, the domain size of the resulting material phases can be finely tuned. Pyrolysis of the printed objects yields ceramics with complex macroscale geometries and nanoscale porosity, which display excellent thermal and oxidation resistance, and morphology-dependent thermal conduction properties. This method offers a valuable technological platform for the simplified fabrication of nanostructured ceramics with complex shapes.

Polymerization Induced Microphase Separation for the Fabrication of Nanostructured Materials.

Polymerization induced microphase separation (PIMS) is a strategy used to develop unique nanostructures with highly useful morphologies through the microphase separation of emergent block copolymers during polymerization. In this process, nanostructures are formed with at least two chemically independent domains, where at least one domain is composed of a robust crosslinked polymer. Crucially, this synthetically simple method is readily used to develop nanostructured materials with the highly coveted co-continuous morphology, which can also be converted into mesoporous materials by selective etching of one domain. As PIMS exploits a block copolymer microphase separation mechanism, the size of each domain can be tightly controlled by modifying the size of block copolymer precursors, thus providing unparalleled control over nanostructure and resultant mesopore sizes. Since its inception 11 years ago, PIMS has been used to develop a vast inventory of advanced materials for an extensive range of applications including biomedical devices, ion exchange membranes, lithium-ion batteries, catalysis, 3D printing, and fluorescence-based sensors, among many others. In this review, we provide a comprehensive overview of the PIMS process, summarize latest developments in PIMS chemistry, and discuss its utility in a wide variety of relevant applications.

Effect of Macromolecular Structure on Phase Separation Regime in 3D Printed Materials.

In this study, the fabrication of 3D-printed polymer materials with controlled phase separation using polymerization induced microphase separation (PIMS) via photoinduced 3D printing is demonstrated. While many parameters affecting the nanostructuration in PIMS processes are extensively investigated, the influence of the chain transfer agent (CTA) end group, i.e., Z-group, of macromolecular chain transfer agent (macroCTA) remains unclear as previous research has exclusively employed trithiocarbonate as the CTA end group. Herein, the effect of macroCTAs containing four different Z-groups on the formation of nanostructure of 3D printed materials is explored. The results show that the different Z-groups lead to distinct network formation and phase separation behaviors between the resins, influencing both the 3D printing process and the resulting material properties. Specifically, less reactive macroCTAs toward acrylic radical addition, such as O-alkyl xanthate and N-alkyl-N-aryl dithiocarbamate, result in translucent and brittle materials with macrophase separation morphology. In contrast, more reactive macroCTAs such as S-alkyl trithiocarbonate and 4-chloro-3,5-dimethylpyrazo dithiocarbamate produce transparent and rigid materials with nano-scale morphology. Findings of this study provide a novel approach to manipulate the nanostructure and properties of 3D printed PIMS materials, which can have important implications for materials science and engineering.

Photo-RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light-Regulated Healable Hydrogels under NIR Irradiation.

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS4 - ) in the presence of peroxides. Taking advantage of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non-transparent biological barriers. Notably, the RAFT agents embedded in these hydrogel networks can be reactivated on-demand, enabling the hydrogel healing under NIR light irradiation. In contrast to the minimal healing capability (<15 %) of hydrogels prepared by free radical polymerization (FRP), RAFT-mediated networks display more than 80 % recovery of tensile strength. Although healable polymer networks under UV and blue lights have already been established, this work is the first photochemistry system using NIR light, facilitating photoinduced healing of hydrogels through thick non-transparent barriers.

3D Printed Solid Polymer Electrolytes with Bicontinuous Nanoscopic Domains for Ionic Liquid Conduction and Energy Storage.

Solid polymer electrolytes (SPEs) offer several advantages compared to their liquid counterparts, and much research has focused on developing SPEs with enhanced mechanical properties while maintaining high ionic conductivities. The recently developed polymerization-induced microphase separation (PIMS) technique offers a straightforward pathway to fabricate bicontinuous nanostructured materials in which the mechanical properties and conductivity can be independently tuned. In this work SPEs with tunable mechanical properties and conductivities are prepared via digital light processing 3D printing, exploiting the PIMS process to achieve nanostructured ion-conducting materials for energy storage applications. A rigid crosslinked poly(isobornyl acrylate-stat-trimethylpropane triacrylate) scaffold provided materials with room temperature shear modulus above 400 MPa, while soft poly(oligoethylene glycol methyl ether acrylate) domains containing the ionic liquid 1-butyl-3-methylimidazolium bis-(trifluoromethyl sulfonyl)imide endowed the material with ionic conductivity up to 1.2 mS cm-1 at 30 °C. These features make the 3D-printed SPE very competitive for applications in all solid energy storage devices, including supercapacitors.

Diblock Copolymer Stabilized Liquid Metal Nanoparticles: Particle Settling Behavior and Application to 3D Printing.

Eutectic gallium indium (EGaIn) is a liquid metal with promising applications due to its favorable thermal and electrical conductivity, low viscosity, and metallic nature. For applications, including imaging, catalysis, and nanomedicine, stable EGaIn particles with submicron diameters are required. However, the low viscosity and high density of EGaIn have typically precluded the formation of stable submicron particles due to rapid EGaIn droplet coalescence. In this work, we show that poly(acrylic acid)-block-poly(N,N'-dimethylacrylamide) copolymers are able to effectively stabilize EGaIn nanodroplets formed upon ultrasonication, where the poly(acrylic acid) block anchors the polymer to the EGaIn surface and the poly(N,N'-dimethylacrylamide) block provides colloidal stability to the particles in solution. Although the high density of EGaIn causes rapid particle settling, the behavior is predictable, which allows the average particle size to be controlled through centrifugation. We demonstrate that stable EGaIn particles with sizes on the order of 50-100 nm and narrow particle size distributions can be easily obtained using this method and further used in photopolymer resins to prepare 3D printed EGaIn-polymer hybrid materials. The predictable sizes and high stability of these EGaIn nanoparticles should allow further applications in soft-electronics, nanomedicine, catalysis, and other nanotechnology.

An aqueous photo-controlled polymerization under NIR wavelengths: synthesis of polymeric nanoparticles through thick barriers.

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system using tetrasulfonated zinc phthalocyanine (ZnPcS4 -) as a photocatalyst. Owing to the high catalytic efficiency and excellent oxygen tolerance of this system, well-controlled polyacrylamides, polyacrylates, and polymethacrylates were synthesized at fast rates without requiring deoxygenation. Notably, NIR wavelengths possess enhanced light penetration through non-transparent barriers compared to UV and visible light, allowing high polymerization rates through barriers. Using 6.0 mm pig skin as a barrier, the polymerization rate was only reduced from 0.36 to 0.21 h-1, indicating potential for biomedical applications. Furthermore, longer wavelengths (higher λ) can be considered an ideal light source for dispersion photopolymerization, especially for the synthesis of large diameter (d) nanoparticles, as light scattering is proportional to d 6/λ 4. Therefore, this aqueous photo-RAFT system was applied to photoinduced polymerization-induced self-assembly (photo-PISA), enabling the synthesis of polymeric nanoparticles with various morphologies, including spheres, worms, and vesicles. Taking advantage of high penetration and reduced light scattering of NIR wavelengths, we demonstrate the first syntheses of polymeric nanoparticles with consistent morphologies through thick barriers.

3D Printing Nanostructured Solid Polymer Electrolytes with High Modulus and Conductivity.

The development of advanced solid-state energy-storage devices is contingent upon finding new ways to produce and manufacture scalable, high-modulus solid-state electrolytes that can simultaneously provide high ionic conductivity and robust mechanical integrity. In this work, an efficient one-step process to manufacture solid polymer electrolytes composed of nanoscale ion-conducting channels embedded in a rigid crosslinked polymer matrix via Digital Light Processing 3D printing is reported. A visible-light-mediated polymerization-induced microphase-separation approach is utilized, which produces materials with two chemically independent nanoscale domains with highly tunable nanoarchitectures. By producing materials containing a poly(ethylene oxide) domain swelled with an ionic liquid, robust solid polymer electrolytes with outstanding room-temperature (22 °C) shear modulus (G' > 108 Pa) and ionic conductivities up to σ = 3 × 10-4 S cm-1 are achieved. The nanostructured 3D-printed electrolytes are fabricated into a custom geometry and employed in a symmetric carbon supercapacitor, demonstrating the scalability of the fabrication and the functionality of the electrolyte. Critically, these high-performance materials are manufactured on demand using inexpensive and commercially available 3D printers, which allows the facile modular design of solid polymer electrolytes with custom geometries.

Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture.

Nanostructured polymeric materials play important roles in many advanced applications, however, controlling the morphologies of polymeric thermosets remains a challenge. This work uses multi-arm macroCTAs to mediate polymerization-induced microphase separation (PIMS) and prepare nanostructured materials via photoinduced 3D printing. The characteristic length scale of microphase-separated domains is determined by the macroCTA arm length, while nanoscale morphologies are controlled by the macroCTA architecture. Specifically, using 2- and 4- arm macroCTAs provides materials with different morphologies compared to analogous monofunctional linear macroCTAs at similar compositions. The mechanical properties of these nanostructured thermosets can also be tuned while maintaining the desired morphologies. Using multi-arm macroCTAs can thus broaden the scope of accessible nanostructures for extended applications, including the fabrication of actuators and potential drug delivery devices.

Nano- to macro-scale control of 3D printed materials via polymerization induced microphase separation.

Although 3D printing allows the macroscopic structure of objects to be easily controlled, controlling the nanostructure of 3D printed materials has rarely been reported. Herein, we report an efficient and versatile process for fabricating 3D printed materials with controlled nanoscale structural features. This approach uses resins containing macromolecular chain transfer agents (macroCTAs) which microphase separate during the photoinduced 3D printing process to form nanostructured materials. By varying the chain length of the macroCTA, we demonstrate a high level of control over the microphase separation behavior, resulting in materials with controllable nanoscale sizes and morphologies. Importantly, the bulk mechanical properties of 3D printed objects are correlated with their morphologies; transitioning from discrete globular to interpenetrating domains results in a marked improvement in mechanical performance, which is ascribed to the increased interfacial interaction between soft and hard domains. Overall, the findings of this work enable the simplified production of materials with tightly controllable nanostructures for broad potential applications.

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization.

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties dependent on the chemical composition of the resin. In the current work, 3D printed materials are post-functionalized using the 3D printer hardware via a secondary surface-initiated polymerization process, thus providing independent control over the bulk and interfacial material properties. This process begins with preparing liquid resins, which contain a monofunctional monomer, a crosslinking multifunctional monomer, a photochemically labile species that enables initiation of polymerization, and critically, a thiocarbonylthio compound which facilitates reversible addition-fragmentation chain transfer (RAFT) polymerization. The thiocarbonylthio compound, known commonly as a RAFT agent, mediates the chain growth polymerization process and provides polymeric materials with more homogeneous network structures. The liquid resin is cured in a layer-by-layer fashion using a commercially available digital light processing 3D printer to give three-dimensional materials having spatially controlled geometries. The initial resin is removed and replaced with a new mixture containing functional monomers and photoinitiating species. The 3D printed material is then exposed to light from the 3D printer in the presence of the new functional monomer mixture. This allows photoinduced surface-initiated polymerization to occur from the latent RAFT agent groups on the surface of the 3D printed material. Given the chemical flexibility of both resins, this process allows a wide range of 3D printed materials to be produced with tailorable bulk and interfacial properties.

Rational Design of Photocatalysts for Controlled Polymerization: Effect of Structures on Photocatalytic Activities.

Over the past decade, the use of photocatalysts (PCs) in controlled polymerization has brought new opportunities in sophisticated macromolecular synthesis. However, the selection of PCs in these systems has been typically based on laborious trial-and-error strategies. To tackle this limitation, computer-guided rational design of PCs based on knowledge of structure-property-performance relationships has emerged. These rational strategies provide rapid and economic methodologies for tuning the performance and functionality of a polymerization system, thus providing further opportunities for polymer science. This review provides an overview of PCs employed in photocontrolled polymerization systems and summarizes their progression from early systems to the current state-of-the-art. Background theories on electronic transitions are also introduced to establish the structure-property-performance relationships from a perspective of quantum chemistry. Typical examples for each type of structure-property relationships are then presented to enlighten future design of PCs for photocontrolled polymerization.

Bioactive Synthetic Polymers.

Synthetic polymers are omnipresent in society as textiles and packaging materials, in construction and medicine, among many other important applications. Alternatively, natural polymers play a crucial role in sustaining life and allowing organisms to adapt to their environments by performing key biological functions such as molecular recognition and transmission of genetic information. In general, the synthetic and natural polymer worlds are completely separated due to the inability for synthetic polymers to perform specific biological functions; in some cases, synthetic polymers cause uncontrolled and unwanted biological responses. However, owing to the advancement of synthetic polymerization techniques in recent years, new synthetic polymers have emerged that provide specific biological functions such as targeted molecular recognition of peptides, or present antiviral, anticancer, and antimicrobial activities. In this review, the emergence of this generation of bioactive synthetic polymers and their bioapplications are summarized. Finally, the future opportunities in this area are discussed.

A Photoinduced Dual-Wavelength Approach for 3D Printing and Self-Healing of Thermosetting Materials.

Vat photopolymerization-based 3D printing techniques have been widely used to produce high-resolution 3D thermosetting materials. However, the lack of repairability of these thermosets leads to the production of waste. In this study, reversible addition fragmentation chain transfer (RAFT) agents are incorporated into resin formulations to allow visible light (405 nm) mediated 3D printing of materials with self-healing capabilities. The self-healing process is based on the reactivation of RAFT agent embedded in the thermosets under UV light (365 nm), which enables reformation of the polymeric network. The self-healing process can be performed at room temperature without prior deoxygenation. The impact of the type and concentration of RAFT agents in the polymer network on the healing efficiency is explored. Resins containing RAFT agents enable 3D printing of thermosets with self-healing properties, broadening the scope of future applications for polymeric thermosets in various fields.

Nanostructure Control in 3D Printed Materials.

Currently, there are no straightforward methods to 3D print materials with nanoscale control over morphological and functional properties. Here, a novel approach for the fabrication of materials with controlled nanoscale morphologies using a rapid and commercially available Digital Light Processing 3D printing technique is demonstrated. This process exploits reversible deactivation radical polymerization to control the in-situ-polymerization-induced microphase separation of 3D printing resins, which provides materials with complex architectures controllable from the macro- to nanoscale, resulting in the preparation of materials with enhanced mechanical properties. This method does not require specialized equipment or process conditions and thus represents an important development in the production of advanced materials via additive manufacturing.

Photo-Enhanced Antimicrobial Activity of Polymers Containing an Embedded Photosensitiser.

This work presents the synthesis of a novel photosensitive acrylate monomer for use as both a self-catalyst in the photoinduced electron/energy transfer-reversible addition fragmentation chain transfer (PET-RAFT) polymerisation process and a photosensitiser (PS) for antibacterial applications. Hydrophilic, cationic, and antimicrobial formulations are explored to compare the antibacterial effects between charged and non-charged polymers. Covalent attachment of the catalyst to well-defined linear polymer chains has no effect on polymerisation control or singlet oxygen generation. The addition of the PS to polymers provides activity against S. aureus for all polymer formulations, resulting in up to a 99.99999 % killing efficacy in 30 min. Antimicrobial peptide mimetic polymers previously active against P. aeruginosa, but not S. aureus, gain significant bactericidal activity against S. aureus through the inclusion of PS groups, with 99.998 % killing efficiency after 30 min incubation with light. Thus, a broader spectrum of antimicrobial activity is achieved using two distinct mechanisms of bactericidal activity via the incorporation of a photosensitiser monomer into an antimicrobial polymer.