Stereolithography printing of ceramics and glass relies on compositions containing dispersed particles in photopolymerizable solutions. A new approach based on utilizing sol–gel precursor solutions has been introduced in recent years, which overcomes challenges in particle-based printing compositions, such as light scattering, particle sedimentation, and high viscosity. Following sol–gel and photopolymerization processes’ combination, this paper presents the methodologies for the 3D printing of complex ceramics and glass structures. This combination allows precise structure control, enabling dense or porous objects, transparent forms, and simple doping. These advantages are presented through the fabrication of porous γ-alumina, transparent silica glass, and chromium-doped α-alumina.

This study explores the utilization of digital light processing (DLP) printing to fabricate complex structures using native gelatin as the sole structural component for applications in biological implants. Unlike approaches relying on synthetic materials or chemically modified biopolymers, this research harnesses the inherent properties of gelatin to create biocompatible structures. The printing process is based on a crosslinking mechanism using a di-tyrosine formation initiated by visible light irradiation. Formulations containing gelatin were found to be printable at the maximum documented concentration of 30 wt%, thus allowing the fabrication of overhanging objects and open embedded. Cell adhesion and growth onto and within the gelatin-based 3D constructs were evaluated by examining two implant fabrication techniques: (1) cell seeding onto the printed scaffold and (2) printing compositions that contain cells (cell-laden). The preliminary biological experiments indicate that both the cell-seeding and cell-laden strategies enable making 3D cultures of chondrocytes within the gelatin constructs. The mechanical properties of the gelatin scaffolds have a compressive modulus akin to soft tissues, thus enabling the growth and proliferation of cells, and later degrade as the cells differentiate and form a grown cartilage. This study underscores the potential of utilizing non-modified protein-only bioinks in DLP printing to produce intricate 3D objects with high fidelity, paving the way for advancements in regenerative tissue engineering.

Adjustable wettability is important for various fields, such as droplet manipulation and controlled surface adhesion. Herein, we present high-resolution 3D stretchable structures with tunable superhydrophobicity, fabricated by a stereolithography-based printing process. The printing compositions comprise nonfluorinated monomers based on silicone urethane with dispersed hydrophobic silica particles. 3D lotus-like structures were designed and printed, having microsize pillars located at the external surfaces, with controlled dimensions and interspacing. The design of the pillars and the presence of the hydrophobic silica particles resulted in superhydrophobicity due to the surface structuring and entrapment of air between the pillars. The best structures display a contact angle of 153.3° ± 1.3° and rolling angle of 3.3° ± 0.5°, and their self-cleaning, water repellency, and buoyancy are demonstrated. The durability of the structure over time, water immersion, and heat exposure were tested, confirming the preservation of superhydrophobicity under these conditions. Upon stretching the surfaces, the interpillar distances change, thus enabling tuning the wetting properties and achieving good control over the contact and rolling angles, while the stretching-induced superhydrophobicity is reversible. This approach can expand the potential applications of superhydrophobic soft materials to fields requiring control over the wetting properties, including soft robotics, biomedical devices, and stretchable electronics.

A novel approach, i.e., Continuous Material Deposition on Filaments (CMDF), for the incorporation of active materials within 3D-printed structures is presented. It is based on passing a filament through a solution in which the active material is dissolved together with the polymer from which the filament is made. This enables the fabrication of a variety of functional 3D-printed objects by fused deposition modeling (FDM) using commercial filaments without post-treatment processes. This generic approach has been demonstrated in objects using three different types of materials, Rhodamine B, ZnO nanoparticles (NPs), and Ciprofloxacin (Cip). The functionality of these objects is demonstrated through strong antibacterial activity in ZnO NPs and the controlled release of the antibiotic Cip. CMDF does not alter the mechanical properties of FDM-printed structures, can be applied with any type of FDM printer, and is, therefore, expected to have applications in a wide variety of fields.

Piezoelectric materials have found widespread use in miniaturized sensors and actuators due to their ability of mutual conversion of mechanical and electric energy. However, current fabrication techniques for these materials are limited to either bulky structures or thin films, restricting the potential that could arise from developing devices with more intricate geometries. Here, we have developed particle-free piezoelectric ink and successfully employed in 3D printing complex barium titanate (BTO) devices using Digital Light Processing technology. The sol–gel process overcomes the viscosity and light scattering issues associated with the slurry traditionally used in 3D printing of piezoelectric ceramic materials. Printed BTO exhibits a remarkable piezoelectric coefficient of 50 pm/V and is utilized to create 3D micrometric structures for applications as both active devices, such as actuators, and passive devices, including displacement sensors and energy harvesters. Furthermore, the flexibility in device fabrication enabled us to 3D print metamaterial piezoelectric structures, designed to concentrate mechanical stress, thereby enhancing the electrical response compared to conventional bulk structures. This research not only advances the field by overcoming fabrication challenges but also opens avenues for creating innovative devices. The design freedom afforded by additive manufacturing technology further underscores the potential for groundbreaking developments in this domain.

Many optoelectronic devices, such as solar cells and LEDs, require materials that possess both transparency and conductivity. Indium tin oxide (ITO), the most commonly used transparent conductor, is limited to flat thin films and, therefore, cannot be used in 3D electronics. Herein, we present the fabrication of complex 3D ITO structures at sub-micron resolution via multiphoton absorption polymerization (MAP), a vat photopolymerization technology, by combining sol-gel chemistry and radical polymerization. Following the MAP fabrication, heat treatment is applied to convert the gel into a ceramic ITO. The sintering temperature affects the porosity, electrical conductivity, and transparency of the printed ITO structures. Electrical conductivity was measured for printed objects sintered at temperatures starting at 700 °C up to 1150 °C with a maximum bulk conductivity of 14.47 ± 1.54 S/cm at 1000 °C and maximal transparency above 90 %. Enabling the fabrication of full 3D conductive ITO micro-structures via MAP, this work unlocks new possibilities and perspectives for the fabrication of 3D optoelectronic devices with transparent and conductive components.

Traditional printing compositions for stereolithography (SLA), a vat photopolymerization technology, rely on light-sensitive photoinitiators (PIs) to initiate cross-linking reactions. Here, we propose a new approach for printing in which the polymerisation occurs locally with carbon nanotubes (CNTs), which function as photothermal converters combined with low-cost thermal initiators (TIs). The irradiation is performed at near-infrared (NIR), which enables deep light penetration, and polymerisation in black compositions, thus increasing the printing throughput. We demonstrate the control over polymerisation kinetics, printing resolution and cure depth, achieving very large printable layer thickness. The CNT photoconvertors can be used in both nonaqueous and aqueous systems, while the latter addresses the limited availability of water-soluble PIs for printing in water. The CNT enables dual use, initiating polymerisation and printing composite materials. This approach presents an advancement in SLA-based technologies, avoiding the use of conventional PIs and thus broadening the scope of 3D printing applications.

A novel method is presented for fabricating 3D-printed Cr³⁺-doped α-Al₂O₃ complex structures, known as Ruby, using digital light processing (DLP) 3D printing and sol-gel reactions based on solutions only. The aqueous printing solution comprises aluminum and chromium chloride as the sol-gel precursor and acrylic acid (AA) as the polymerizable component. After photopolymerization, aging, and sintering at 1150°C, structures shrink up to 28±7%, achieving a final printing resolution of 55.7±0.7 μm, surpassing the nominal printer’s resolution of 200 μm. Characterization includes X-ray diffraction, scanning electron microscopy, UV-Vis, and fluorescence measurements, revealing crystalline Cr:α-Al₂O₃ composition emitting at 693 nm. The structures exhibit maximum compression stress of 89±3 MPa and microhardness of 340-500 HV, showcasing potential applications in thermal insulation, jewelry, and mechanical uses.

Rapid deployment of automation in today's world has opened up exciting possibilities in the realm of design and fabrication of soft robotic grippers endowed with sensing capabilities. Herein, a novel design and rapid fabrication by 3D printing of a mechano-optic force sensor with a large dynamic range, sensitivity, and linear response, enabled by metamaterials-based structures, is presented. A simple approach for programming the metamaterial's behavior based on mathematical modeling of the sensor under dynamic loading is proposed. Machine learning models are utilized to predict the complete force–deformation profile, encompassing the linear range, the onset of nonlinear behavior, and the slope of profiles in both bending and compression-dominated regions. The design supports seamless integration of the sensor into soft grippers, enabling 3D printing of the soft gripper with an embedded sensor in a single step, thus overcoming the tedious and complex and multiple fabrication steps commonly applied in conventional processes. The sensor boasts a fine resolution of 0.015 N, a measurement range up to 16 N, linearity (adj. R²–0.991), and delivers consistent performance beyond 100 000 cycles. The sensitivity and range of the embedded mechano-optic force sensor can be easily programmed by both the metamaterial structure and the material's properties.

Soft grippers are garnering increasing attention for their adeptness in conforming to diverse objects, particularly delicate items, without warranting precise force control. This attribute proves especially beneficial in unstructured environments and dynamic tasks such as food handling. Human hands, owing to their elevated dexterity and precise motor control, exhibit the ability to delicately manipulate complex food items, such as small or fragile objects, by dynamically adjusting their grasping configurations. Furthermore, with their rich sensory receptors and hand-eye coordination that provide valuable information involving the texture and form factor, real-time adjustments to avoid damage or spill during food handling appear seamless. Despite numerous endeavors to replicate these capabilities through robotic solutions involving soft grippers, matching human performance remains a formidable engineering challenge. Robotic competitions serve as an invaluable platform for pushing the boundaries of manipulation capabilities, simultaneously offering insights into the adoption of these solutions across diverse domains, including food handling. Serving as a proxy for the future transition of robotic solutions from the laboratory to the market, these competitions simulate real-world challenges. Since 2021, our research group has actively participated in RoboSoft competitions, securing victories in the Manipulation track in 2022 and 2023. Our success was propelled by the utilization of a modified iteration of our Retractable Nails Soft Gripper (RNSG), tailored to meet the specific requirements of each task. The integration of sensors and collaborative manipulators further enhanced the gripper’s performance, facilitating the seamless execution of complex grasping tasks associated with food handling. This article encapsulates the experiential insights gained during the application of our highly versatile soft gripper in these competition environments.

Hybrid perovskites show piezoelectric properties due to polarization and centro-symmetry breaking of PbX₆ pyramids (X = I-, Br-, Cl-). This study examines the piezoelectric response of quasi-2D perovskites using various barrier molecules: benzyl amine (BzA), phenylethyl amine (PEA), and butyl diamine (BuDA). Utilizing piezoelectric force microscopy measurements, we determine the piezoelectric coefficient (d₃₃) where BuDA exhibits a substantial response with values of 147 pm V^–1 for n = 5, better than the other quasi-2D and 3D perovskite counterparts. Density functional theory calculations reveal distorted bond angles in the PbBr₆ pyramids for quasi-2D perovskites, enhancing symmetry breaking. Additionally, polarizabilities and dielectric constants, derived from ab initio many-body perturbation theory, are highest for BuDA, followed by PEA and BzA, aligning with experimental results. We demonstrate pressure sensor performance, emphasizing the quicker capacitance decay time of the quasi-2D perovskite based on BuDA. This research underscores the impact of perovskite dimensionality on piezoelectricity, paving the way for the development of sensitive and wide-ranging pressure sensors.

Additive manufacturing technologies based on stereolithography rely on initiating spatial photopolymerization by using photoinitiators activated by UV-visible light. Many applications requiring printing in water are limited since water-soluble photoinitiators are scarce, and their price is skyrocketing. On the contrary, thermal initiators are widely used in the chemical industry for polymerization processes due to their low cost and simplicity of initiation by heat at low temperatures. However, such initiators were never used in 3D printing technologies, such as vat photopolymerization stereolithography, since localizing the heat at specific printing voxels is impossible. Here we propose using a thermal initiator for 3D printing for localized polymerization processes by near-infrared and visible light irradiation without conventional photoinitiators. This is enabled by using gold nanorods or silver nanoparticles at very low concentrations as photothermal converters in aqueous and non-aqueous mediums. Our proof of concept demonstrates the fabrication of hydrogel and polymeric objects using stereolithography-based 3D printers, vat photopolymerization, and two-photon printing.

The median survival time of patients with an aggressive brain tumor, glioblastoma, is still poor due to ineffective treatment. The discovery of androgen receptor (AR) expression in 56% of cases offers a potential breakthrough. AR antagonists, including bicalutamide and enzalutamide, induce dose-dependent cell death in glioblastoma and glioblastoma-initiating cell lines (GIC). Oral enzalutamide at 20 mg/kg reduces subcutaneous human glioblastoma xenografts by 72% (p = 0.0027). We aimed to further investigate the efficacy of AR antagonists in intracranial models of human glioblastoma. In U87MG intracranial models, nude mice administered Xtandi (enzalutamide) at 20 mg/kg and 50 mg/kg demonstrated a significant improvement in survival compared to the control group (p = 0.24 and p < 0.001, respectively), confirming a dose–response relationship. Additionally, we developed a newly reformulated version of bicalutamide, named “soluble bicalutamide (Bic-sol)”, with a remarkable 1000-fold increase in solubility. This reformulation significantly enhanced bicalutamide levels within brain tissue, reaching 176% of the control formulation’s area under the curve. In the U87MG intracranial model, both 2 mg/kg and 4 mg/kg of Bic-sol exhibited significant efficacy compared to the vehicle-treated group (p = 0.0177 and p = 0.00364, respectively). Furthermore, combination therapy with 8 mg/kg Bic-sol and Temozolomide (TMZ) demonstrated superior efficacy compared to either Bic-sol or TMZ as monotherapies (p = 0.00706 and p = 0.0184, respectively). In the ZH-161 GIC mouse model, the group treated with 8 mg/kg Bic-sol as monotherapy had a significantly longer lifespan than the groups treated with TMZ or the vehicle (p < 0.001). Our study demonstrated the efficacy of androgen receptor antagonists in extending the lifespan of mice with intracranial human glioblastoma, suggesting a promising approach to enhance patient outcomes in the fight against this challenging disease.

This review article presents a comprehensive overview of the latest advances in the field of 3D printable structures with self-healing properties. Three-dimensional printing (3DP) is a versatile technology that enables the rapid manufacturing of complex geometric structures with precision and functionality not previously attainable. However, the application of 3DP technology is still limited by the availability of materials with customizable properties specifically designed for additive manufacturing. The addition of self-healing properties within 3D printed objects is of high interest as it can improve the performance and lifespan of structural components, and even enable the mimicking of living tissues for biomedical applications, such as organs printing. The review will discuss and analyze the most relevant results reported in recent years in the development of self-healing polymeric materials that can be processed via 3D printing. After introducing the chemical and physical self-healing mechanism that can be exploited, the literature review here reported will focus in particular on printability and repairing performances. At last, actual perspective and possible development field will be critically discussed.

Fabrication of glass with complex geocd the low resolution of particle-based or fused glass technologies. Herein, a high-resolution 3D printing of transparent nanoporous glass is presented, by the combination of transparent photo-curable sol–gel printing compositions and digital light processing (DLP) technology. Multi-component glass, including binary (Al₂O₃-SiO₂), ternary (ZnO-Al₂O₃-SiO₂, TiO₂-Al₂O₃-SiO₂), and quaternary oxide (CaO-P₂O₅-Al₂O₃-SiO₂) nanoporous glass objects with complex shapes, high spatial resolutions, and multi-oxide chemical compositions are fabricated, by DLP printing and subsequent sintering process. The uniform nanopores of Al₂O₃-SiO₂-based nanoporous glasses with the diameter (≈6.04 nm), which is much smaller than the visible light wavelength, result in high transmittance (>95%) at the visible range. The high surface area of printed glass objectives allows post-functionalization via the adsorption of functional guest molecules. The photoluminescence and hydrophobic modification of 3D printed glass objectives are successfully demonstrated. This work extends the scope of 3D printing to transparent nanoporous glasses with complex geometry and facile functionalization, making them available for a wide range of applications.

The most prevalent materials used in the Additive Manufacturing era are polymers and plastics. Unfortunately, these materials are recognized for their negative environmental impact as they are primarily nonrecyclable, resulting in environmental pollution. In recent years, a new sustainable alternative to these materials has been emerging: Reversible Covalent Bond-Containing Polymers (RCBPs). These materials can be recycled, reprocessed, and reused multiple times without losing their properties. Nonetheless, they have two significant drawbacks when used in 3D printing. First, some require adding new materials every reprinting cycle, and second, others require high temperatures for (re)printing, limiting recyclability, and increasing energy consumption. This study, thus, introduces fully recyclable RCBPs as a sustainable approach for radiation-based printing technologies. This approach enables multiple (re)printing cycles at low temperatures (50 °C lower than the lowest reported) without adding new materials. It involves purposefully synthesized polymers that undergo reversible photopolymerization, composed of a tin-based catalyst. An everyday microwave oven quickly depolymerized these polymers, obtaining complete reversibility.

Nanocomposites are constructed from a matrix material combined with dispersed nanosized filler particles. Such a combination yields a powerful ability to tailor the desired mechanical, optical, electrical, thermodynamic, and antimicrobial material properties. Colloidal semiconductor nanocrystals (SCNCs) are exciting potential fillers, as they display size-, shape-, and composition-controlled properties and are easily embedded in diverse matrices. Here we present their role as quantum photoinitiators (QPIs) in acrylate-based polymer, where they act as a catalytic radical initiator and endow the system with mechanical, photocatalytic, and antimicrobial properties. By utilizing ZnO nanorods (NRs) as QPIs, we were able to increase the tensile strength and elongation at break of poly(ethylene glycol) diacrylate (PEGDA) hydrogels by up to 85%, unlike the use of the same ZnO NRs acting merely as fillers. Simultaneously, we endowed the PEGDA hydrogels with post-polymerization photocatalytic and antimicrobial activities and showed their ability to decompose methylene blue and significantly eradicate antibiotic-resistant bacteria and viral pathogens. Moreover, we demonstrate two fabrication showcase methods, traditional molding and digital light processing printing, that can yield hydrogels with complex architectures. These results position SCNC-based systems as promising candidates to act as all-in-one photoinitiators and fillers in nanocomposites for diverse biomedical applications, where specific and purpose-oriented characteristics are required.

Resilin is an elastic rubber-like protein found in the cuticles of insects. It incorporates outstanding properties of high resilience and fatigue lifetime, where kinetic energy storage is needed for biological functions such as flight and jumps. Since resilin is rich in tyrosine groups, localized photopolymerization is enabled due to the ability to introduce di-tyrosine bonds by a ruthenium-based photoinitiator. Using Multiphoton Absorption Polymerization 3D printing process, objects containing 100% recombinant resilin protein are printed in water at a submicron length scale. Consequently, protein-based hydrogels with complex structures are printed using space positioning voxel polymerization. The objects are characterized by dynamic mechanical analysis using nanoindentation. Printing parameters such as printing speed and laser power are found to enable tuning the mechanical properties of the printed objects. The printed objects are soft and resilient, similar to native resilin, while presenting the highest resolution of a structure made entirely of a protein and better mechanical properties of common hydrogels and poly(dimethylsiloxane). Moreover, topography and mechanical properties enable cell growth and alignment without cell adhesion primers, thus facilitating biological applications. The fabrication of 3D resilin-based hydrogel will open the way for potential applications based on biomimicking and in creating new functional objects.

UV-curable 3D printing compositions for the fabrication of stretchable and flexible porous structures for soft robotics are presented. The stereolithography-based printing compositions are water-in-oil (W/O) emulsions in which water droplets are the pore-forming material, and the continuous phase is a stretchable polyurethane diacrylate (PUA). The porosity of the printed objects is controlled by the material's micro-porosity and by the macro-porosity obtained by a cellular design. The mechanical behavior can be tailored by the composition of the emulsion, providing both compliance and strength while utilizing a unique optimization methodology for fitting the ink to the 3D printer. This approach enables developing materials having superior mechanical properties, with the highest reported elongation-at-break for 3D printed porous structures, 450%. The emulsion-based printing compositions were utilized for fabricating a soft robotic gripper with unique actuation performance that could not be obtained with commonly used materials.