Digital Light 3D Printing of Double Thermoplastics with Customizable Mechanical Properties and Versatile Reprocessability.

Digital light processing (DLP) is a 3D printing technology offering high resolution and speed. Printable materials are commonly based on multifunctional monomers, resulting in the formation of thermosets that usually cannot be reprocessed or recycled. Some efforts are made in DLP 3D printing of thermoplastic materials. However, these materials exhibit limited and poor mechanical properties. Here, a new strategy is presented for DLP 3D printing of thermoplastics based on a sequential construction of two linear polymers with contrasting (stiff and flexible) mechanical properties. The inks consist of two vinyl monomers, which lead to the stiff linear polymer, and α-lipoic acid, which forms the flexible linear polymer via thermal ring-opening polymerization in a second step. By varying the ratio of stiff and flexible linear polymers, the mechanical properties can be tuned with Young's modulus ranging from 1.1 GPa to 0.7 MPa, while the strain at break increased from 4% to 574%. Furthermore, these printed thermoplastics allow for a variety of reprocessability pathways including self-healing, solvent casting, reprinting, and closed-loop recycling of the flexible polymer, contributing to the development of a sustainable materials economy. Last, the potential of the new material in applications ranging from soft robotics to electronics is demonstrated.

Minimal-Invasive 3D Laser Printing of Microimplants in Organismo.

Multi-photon 3D laser printing has gathered much attention in recent years as a means of manufacturing biocompatible scaffolds that can modify and guide cellular behavior in vitro. However, in vivo tissue engineering efforts have been limited so far to the implantation of beforehand 3D printed biocompatible scaffolds and in vivo bioprinting of tissue constructs from bioinks containing cells, biomolecules, and printable hydrogel formulations. Thus, a comprehensive 3D laser printing platform for in vivo and in situ manufacturing of microimplants raised from synthetic polymer-based inks is currently missing. Here, a platform for minimal-invasive manufacturing of microimplants directly in the organism is presented by one-photon photopolymerization and multi-photon 3D laser printing. Employing a commercially available elastomeric ink giving rise to biocompatible synthetic polymer-based microimplants, first applicational examples of biological responses to in situ printed microimplants are demonstrated in the teleost fish Oryzias latipes and in embryos of the fruit fly Drosophila melanogaster. This provides a framework for future studies addressing the suitability of inks for in vivo 3D manufacturing. The platform bears great potential for the direct engineering of the intricate microarchitectures in a variety of tissues in model organisms and beyond.

Printing Green: Microalgae-based Materials for 3D Printing with Light.

Microalgae have emerged as sustainable feedstocks due to their ability to fix CO2 during cultivation, rapid growth rates, and capability to produce a wide variety of metabolites. Several microalgae accumulate lipids in high concentrations, especially triglycerides, along with lipid-soluble, photoactive pigments such as chlorophylls and derivatives. Microalgae-derived triglycerides contain longer fatty acid chains with more double bonds on average than vegetable oils, allowing a higher degree of post-functionalization. Consequently, they are especially suitable as precursors for materials that can be used in 3D printing with light. Herein, we present the use of microalgae as "biofactories" to generate materials that can be further 3D printed in high resolution In this study two taxonomically different strains -Odontella aurita (BEA 0921B) and Tetraselmis striata (BEA 1102B)- are identified as suitable microalgae for our purpose The extracts obtained from the microalgae (mainly triglycerides with chlorophyll derivatives) have been functionalized with photopolymerizable groups and used directly as printable materials (inks) without the need for additional photoinitiators. The fabrication of complex 3D microstructures with sub-micron resolution is demonstrated. Notably, the 3D printed materials show biocompatibility. Our findings open new possibilities for the next generation of sustainable, biobased, and biocompatible materials with great potential in life science applications. This article is protected by copyright. All rights reserved.

Multimaterial 3D Laser Printing of Cell-Adhesive and Cell-Repellent Hydrogels.

Here, a straightforward method is reported for manufacturing 3D microstructured cell-adhesive and cell-repellent multimaterials using two-photon laser printing. Compared to existing strategies, this approach offers bottom-up molecular control, high customizability, and rapid and precise 3D fabrication. The printable cell-adhesive polyethylene glycol (PEG) based material includes an Arg-Gly-Asp (RGD) containing peptide synthesized through solid-phase peptide synthesis, allowing for precise control of the peptide design. Remarkably, minimal amounts of RGD peptide (< 0.1 wt%) suffice for imparting cell-adhesiveness, while maintaining identical mechanical properties in the 3D printed microstructures to those of the cell-repellent, PEG-based material. Fluorescent labeling of the RGD peptide facilitates visualization of its presence in cell-adhesive areas. To demonstrate the broad applicability of the system, the fabrication of cell-adhesive 2.5D and 3D structures is shown, fostering the adhesion of fibroblast cells within these architectures. Thus, this approach allows for the printing of high-resolution, true 3D structures suitable for diverse applications, including cellular studies in complex environments.

Characteristics and long-term kinetics of an azobenzene derivative and a donor-acceptor Stenhouse adduct as orthogonal photoswitches.

Light-triggered molecular switches are extensively researched for their applications in medicine, chemistry and material science and, if combined, particularly for their use in multifunctional smart materials, for which orthogonally, i.e. individually, addressable photoswitches are needed. In such a multifunctional mixture, the switching properties, efficiencies and the overall performance may be impaired by undesired mutual dependences of the photoswitches on each other. Within this study, we compare the performance of the pure photoswitches, namely an azobenzene derivative (Azo) and a donor-acceptor Stenhouse adduct (DASA), with the switching properties of their mixture using time-resolved temperature-dependent UV/VIS absorption spectroscopy, time-resolved IR absorption spectroscopy at room temperature and quantum mechanical calculations to determine effective cross sections, switching kinetics as well as activation energies of thermally induced steps. We find slightly improved effective cross sections, percentages of switched molecules and no increased activation barriers of the equimolar mixture compared to the single compounds. Thus, the studied mixture Azo + DASA is very promising for future applications in multifunctional smart materials.

Photochemically Activated 3D Printing Inks: Current Status, Challenges, and Opportunities.

3D printing with light is enabled by the photochemistry underpinning it. Without fine control over the ability to photochemically gate covalent bond formation by the light at a certain wavelength and intensity, advanced photoresists with functions spanning from on-demand degradability, adaptability, rapid printing speeds, and tailored functionality are impossible to design. Herein, recent advances in photoresist design for light-driven 3D printing applications are critically assessed, and an outlook of the outstanding challenges and opportunities is provided. This is achieved by classing the discussed photoresists in chemistries that function photoinitiator-free and those that require a photoinitiator to proceed. Such a taxonomy is based on the efficiency with which photons are able to generate covalent bonds, with each concept featuring distinct advantages and drawbacks.

Recent Advances in Multi-Photon 3D Laser Printing: Active Materials and Applications.

Since the pioneering work of Kawata and colleagues in 1997, multi-photon 3D laser printing, also known as direct laser writing, has made significant advancements in a wide range of fields. Moreover, the development and commercialization of photocurable inks for this technique have expanded rapidly. One of the current trends is the transition from static to active printable materials, often referred to as 4D microprinting, which enables a new degree of control in the printed systems. This review focuses on four primary application areas: microrobotics, optics and photonics, microfluidics, and life sciences, highlighting recent progress and the crucial role of active materials, including liquid crystalline elastomers, hydrogels, shape memory polymers, and composites, among others. It also addresses ongoing challenges and provides insights into the future prospects in the different fields.

Closed-Loop Recyclable Silica-Based Nanocomposites with Multifunctional Properties and Versatile Processability.

Most plastics originate from limited petroleum reserves and cannot be effectively recycled at the end of their life cycle, making them a significant threat to the environment and human health. Closed-loop chemical recycling, by depolymerizing plastics into monomers that can be repolymerized, offers a promising solution for recycling otherwise wasted plastics. However, most current chemically recyclable polymers may only be prepared at the gram scale, and their depolymerization typically requires harsh conditions and high energy consumption. Herein, it reports less petroleum-dependent closed-loop recyclable silica-based nanocomposites that can be prepared on a large scale and have a fully reversible polymerization/depolymerization capability at room temperature, based on catalysis of free aminopropyl groups with the assistance of diethylamine or ethylenediamine. The nanocomposites show glass-like hardness yet plastic-like light weight and toughness, exhibiting the highest specific mechanical strength superior even to common materials such as poly(methyl methacrylate), glass, and ZrO2 ceramic, as well as demonstrating multifunctionality such as anti-fouling, low thermal conductivity, and flame retardancy. Meanwhile, these nanocomposites can be easily processed by various plastic-like scalable manufacturing methods, such as compression molding and 3D printing. These nanocomposites are expected to provide an alternative to petroleum-based plastics and contribute to a closed-loop materials economy.

Recyclable photoresins for light-mediated additive manufacturing towards Loop 3D printing.

Additive manufacturing (AM) of polymeric materials enables the manufacturing of complex structures for a wide range of applications. Among AM methods vat photopolymerization (VP) is desired owing to improved efficiency, excellent surface finish, and printing resolution at the micron-scale. Nevertheless, the major portion of resins available for VP are based on systems with limited or negligible recyclability. Here, we describe an approach that enables the printing of a resin that is amenable to re-printing with retained properties and appearance. To that end, we take advantage of the potential of polythiourethane chemistry, which not only permits the click reaction between polythiols and polyisocyanates in the presence of organic bases, allowing a fast-printing process but also chemical recycling, reshaping, and reparation of the printed structures, paving the way toward the development of truly sustainable recyclable photoprintable resins. We demonstrate that this closed-loop 3D printing process is feasible both at the macroscale and microscale via DLP or DLW, respectively.

Understanding the Optical Properties of Doped and Undoped 9-Armchair Graphene Nanoribbons in Dispersion.

Graphene nanoribbons are one-dimensional stripes of graphene with width- and edge-structure-dependent electronic properties. They can be synthesized bottom-up in solution to obtain precise ribbon geometries. Here we investigate the optical properties of solution-synthesized 9-armchair graphene nanoribbons (9-aGNRs) that are stabilized as dispersions in organic solvents and further fractionated by liquid cascade centrifugation (LCC). Absorption and photoluminescence spectroscopy reveal two near-infrared absorption and emission peaks whose ratios depend on the LCC fraction. Low-temperature single-nanoribbon photoluminescence spectra suggest the presence of two different nanoribbon species. Based on density functional theory (DFT) and time-dependent DFT calculations, the lowest energy transition can be assigned to pristine 9-aGNRs, while 9-aGNRs with edge-defects, caused by incomplete graphitization, result in more blue-shifted transitions and higher Raman D/G-mode ratios. Hole doping of 9-aGNR dispersions with the electron acceptor F4TCNQ leads to concentration dependent bleaching and quenching of the main absorption and emission bands and the appearance of red-shifted, charge-induced absorption features but no additional emission peaks, thus indicating the formation of polarons instead of the predicted trions (charged excitons) in doped 9-aGNRs.

3D Printing Hierarchically Nano-Ordered Structures.

Natural materials are composed of a limited number of molecular building blocks and their exceptional properties are governed by their hierarchical structure. However, this level of precision is unattainable with current state-of-the-art materials for 3D printing. Herein, new self-assembled printable materials based on block copolymers (BCPs) enabling precise control of the nanostructure in 3D are presented. In particular, well-defined BCPs consisting of poly(styrene) (PS) and a polymethacrylate-based copolymer decorated with printable units are selected as suitable self-assembled materials and synthesized using controlled radical polymerization. The synthesized library of BCPs are utilized as printable formulations for the fabrication of complex 3D microstructures using two-photon laser printing. By fine-tuning the BCP composition and solvent in the formulations, the fabrication of precise 3D nano-ordered structures is demonstrated for the first time. A key point of this work is the achievement of controlled nano-order within the entire 3D structures. Thus, imaging of the cross-sections of the 3D printed samples is performed, enabling the visualization also from the inside. The presented versatile approach is expected to create new avenues for the precise design of functional polymer materials suitable for high-resolution 3D printing exhibiting tailor-made nanostructures.

Macromolecular Engineering: From Precise Macromolecular Inks to 3D Printed Microstructures.

Macromolecules with complex, defined structures exist in nature but rarely is this degree of control afforded in synthetic macromolecules. Sequence-defined approaches provide a solution for precise control of the primary macromolecular structure. Despite a growing interest, very few examples for applications of sequence-defined macromolecules exist. In particular, the use of sequence-defined macromolecules as printable materials remains unexplored. Herein, the rational design of precise macromolecular inks for 3D microprinting is investigated for the first time. Specifically, three printable oligomers are synthesized, consisting of eight units, either crosslinkable (C) or non-functional (B) with varied sequence (BCBCBCBC, alternating; BBCCCBB, triblock; and BBBBCCCC, block). The oligomers are printed using two-photon laser printing and characterized. It is clearly demonstrated that the macromolecular sequence, specifically the positioning of the crosslinkable group, plays a critical role in both the printability and final properties of the printed material. Thus, through precise design and printability of sequence-defined macromolecules, an exciting avenue for the next generation of functional materials for 3D printing is created.

Two Functions from a Single Photoresist: Tuning Microstructure Degradability from Light-Stabilized Dynamic Materials.

A photoresist-based on a light-stabilized dynamic material driven by an out-of-equilibrium photo-Diels-Alder reaction of triazolinediones with naphthalenes-whose ability to intrinsically degrade postprinting can be tuned by a simple adjustment of laser intensity during 3D laser lithography is introduced. The resist's ability to form stable networks under green light irradiation that degrade in the dark is transformed into a tunable degradable 3D printing material platform. In-depth characterization of the printed microstructures via atomic force microscopy before and during degradation reveals the high dependency of the final structures' properties on the writing parameters. Upon identifying the ideal writing parameters and their effect on the network structure, it is possible to selectively toggle between stable and fully degradable structures. This simplifies the direct laser writing manufacturing process of multifunctional materials significantly, which typically requires the use of separate resists and consecutive writing efforts to achieve degradable and nondegradable material sections.

Laser printed microelectronics.

Printed organic and inorganic electronics continue to be of large interest for sensors, bioelectronics, and security applications. Many printing techniques have been investigated, albeit often with typical minimum feature sizes in the tens of micrometer range and requiring post-processing procedures at elevated temperatures to enhance the performance of functional materials. Herein, we introduce laser printing with three different inks, for the semiconductor ZnO and the metals Pt and Ag, as a facile process for fabricating printed functional electronic devices with minimum feature sizes below 1 µm. The ZnO printing is based on laser-induced hydrothermal synthesis. Importantly, no sintering of any sort needs to be performed after laser printing for any of the three materials. To demonstrate the versatility of our approach, we show functional diodes, memristors, and a physically unclonable function based on a 6 × 6 memristor crossbar architecture. In addition, we realize functional transistors by combining laser printing and inkjet printing.

Two-Photon Laser Microprinting of Highly Ordered Nanoporous Materials Based on Hexagonal Columnar Liquid Crystals.

Nanoporous materials relying on supramolecular liquid crystals (LCs) are excellent candidates for size- and charge-selective membranes. However, whether they can be manufactured using printing technologies remained unexplored so far. In this work, we develop a new approach for the fabrication of ordered nanoporous microstructures based on supramolecular LCs using two-photon laser printing. In particular, we employ photo-cross-linkable hydrogen-bonded complexes, that self-assemble into columnar hexagonal (Colh) mesophases, as the base of our printable photoresist. The presence of photopolymerizable groups in the periphery of the molecules enables the printability using a laser. We demonstrate the conservation of the Colh arrangement and of the adsorptive properties of the materials after laser microprinting, which highlights the potential of the approach for the fabrication of functional nanoporous structures with a defined geometry. This first example of printable Colh LC should open new opportunities for the fabrication of functional porous microdevices with potential application in catalysis, filtration, separation, or molecular recognition.

Wavelength-Resolved PhotoATRP.

The careful mapping of photoinduced reversible-deactivation radical polymerizations (RDRP) is a prerequisite for their applications in soft matter materials design. Here, we probe the wavelength-dependent behavior of photochemically induced atom transfer radical polymerization (ATRP) using nanosecond pulsed-laser polymerization (PLP). The photochemical reactivities at identical photon fluxes of methyl acrylate in terms of conversion, number-average molecular weight, and dispersity of the resulting polymers are mapped against the absorption spectrum of the copper(II) catalyst in the range of 305-550 nm. We observe a red shift of the action spectrum relative to the absorption spectrum of the copper(II) catalyst. Both the number-average molecular weight and the dispersity show a wavelength dependence, while the molecular weight and conversion remain linearly correlated. The reported data allow the judicious selection of optimum wavelengths for photoATRP.

UV-induced photolysis of polyurethanes.

Waste production associated with the use of non-degradable materials in packaging is a growing cause of environmental concern, with the polyurethane (PU) class being notorious for their lack of degradability. Herein, we incorporate photosensitive ortho-Nitrobenzyl units into PUs to achieve controllable photodegradability. We performed their photolysis in solution and thin films which can inform the design of degradable adhesives.

Chain-Length-Dependent Photolysis of ortho-Nitrobenzyl-Centered Polymers.

Herein, we demonstrate that the photochemical cleavage of linear polymers containing a midchain photocleavable moiety strongly depends on the chain length. Based on an ortho-nitrobenzyl (oNB) difunctional reversible addition-fragmentation chain-transfer agent, well-defined poly(methyl acrylate)s (Mn = 1.59-67.6 kg mol-1, D = 1.3-1.4) were synthesized following a core-first approach. Photolysis at λmax = 350 nm of the ortho-nitrobenzyl moiety led to the generation of equally sized polymer segments. The rate of oNB-driven polymer fragmentation, which can be well described by first-order kinetics, strongly increases with increasing molecular weight in a nonlinear fashion, potentially caused by entropic considerations and is compared to the ideal chain model. The current study thus demonstrates that polymer photolysis is dependent on the polymer chain length, with critical implications for photocleavable network design.