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Liquid crystal elastomer (LCE)-based soft actuators are being studied for their significant shape-changing abilities when they are exposed to heat or light. Nevertheless, their relatively slow response compared with soft magnetic materials limits their application possibilities. Integration of magnetic responsiveness with LCEs has been previously attempted; however, the LCE response is typically jeopardized in high volumes of magnetic microparticles (MMPs). Here, a multistimuli, magnetically active LCE (MLCE), capable of producing programmable and multimodal actuation, is presented. The MLCE, composed of MMPs within an LCE matrix, is generated through extrusion-based 4D printing that enables digital control of mesogen orientation even at a 1:1 (LCE:MMPs) weight ratio, a challenging task to accomplish with other methods. The printed actuators can significantly deform when thermally actuated as well as exhibit fast response to magnetic fields. When combining thermal and magnetic stimuli, modes of actuation inaccessible with only one input are achieved. For instance, the actuator is reconfigured into various states by using the heat-mediated LCE response, followed by subsequent magnetic addressing. The multistimuli capabilities of the MLCE composite expand its applicability where common LCE actuators face limitations in speed and precision. To illustrate, a beam-steering device developed by using these materials is presented.

Biomimetic 3D models emerged some decades ago to address 2D cell culture limitations in the field of replicating biological phenomena, structures or functions found in nature. The fabrication of hydrogels for cancer disease research enables the study of cell processes including growth, proliferation and migration and their 3D design is based on the encapsulation of tumoral cells within a tunable matrix. In this work, a platform of gelatin methacrylamide (GelMA)-based photocrosslinked scaffolds with embedded colorectal (HCT-116) or pancreatic (MIA PaCa-2) cancer cells is presented. Prior to cell culture, the mechanical characterization of hydrogels was assessed in terms of stiffness and swelling behavior. Modifications of the UV curing time enabled a fine tuning of the mechanical properties, which at the same time, showed susceptibility to the chemical composition and crosslinking mechanism. All scaffolds displayed excellent cytocompatibility with both tumoral cells while eliciting various cell responses depending on the microenvironment features. Individual and collective cell migration were observed for HCT-116 and MIA PaCa-2 cell lines, highlighting the ability of the colorectal cancer cells to cluster into aggregates of different sizes governed by the surrounding matrix. Additionally, metabolic activity results pointed out to the development of a more proliferative phenotype within stiffer networks. These findings confirm the suitability of the presented platform of GelMA-based hydrogels to conduct 3D cell culture experiments and explore biological processes associated with colorectal and pancreatic cancer.

Soft and mechanically responsive actuators hold the promise to revolutionize the design and manufacturing of devices in the areas of microfluidics, soft robotics and biomedical engineering. In many of these applications, the actuators need to operate in a wet environment that can strongly affect their performance. In this paper, we report on the photomechanical response in a biological buffer of azobenzene-containing liquid crystal elastomer (LCE)-based actuators, prepared by four-dimensional (4D) printing. Although the photothermal contribution to the photoresponse is largely cancelled by the heat withdrawing capacity of the employed buffer, a significant photoinduced reversible contraction, in the range of 7% of its initial length, has been achieved under load, taking just a few seconds to reach half of the maximum contraction. Effective photomechanical work performance under physiological conditions has, therefore, been demonstrated in the 4D-printed actuators. Advantageously, the photomechanical response is not sensitive to salts present in the buffer differently to hydrogels with responses highly dependent on the fluid composition. Our work highlights the capabilities of photomechanical actuators, created using 4D printing, when operating under physiological conditions, thus showing their potential for application in the microfluidics and biomedical fields.

Hydrogel preparation protocol; 1H NMR spectra of the non-modified gelatin, GelMA macromer, GelMA and SH hydrogels, and free four-arm poly(ethylene glycol) thiol; and Young’s moduli of SH hydrogels.

The mechanical microenvironment plays a crucial role in the evolution of colorectal cancer, a complex disease characterized by heterogeneous tumors with varying elasticity. Toward setting up distinct scenarios, herein, we describe the preparation and characterization of gelatin methacrylamide (GelMA)-based hydrogels via two different mechanisms: free-radical photopolymerization and photo-induced thiol-ene reaction. A precise stiffness modulation of covalently crosslinked scaffolds was achieved through the application of well-defined irradiation times while keeping the intensity constant. Besides, the incorporation of thiol chemistry strongly increased stiffness with low to moderate curing times. This wide range of finely tuned mechanical properties successfully covered from healthy tissue to colorectal cancer stages. Hydrogels prepared in phosphate-buffered saline or Dulbecco’s modified Eagle’s medium resulted in different mechanical and swelling properties, although a similar trend was observed for both conditions: thiol-ene systems exhibited higher stiffness and, at the same time, higher swelling capacity than free-radical photopolymerized networks. In terms of biological behavior, three of the substrates showed good cell proliferation rates according to the formation of a confluent monolayer of Caco-2 cells after 14 days of cell culture. Likewise, a characteristic apical-basal polarization of cells was observed for these three hydrogels. These results demonstrate the versatility of the presented platform of biomimetic materials as in vitro cell culture scaffolds.

Recent years have seen major advances in the additive manufacturing of stimuli-responsive materials, also known as “4D printing,” among which liquid crystal elastomers (LCEs) play an important role. However, during fabrication photo-crosslinking of the LCEs is required, but this step is time-consuming and efficient polymerization is challenging, especially in the case of light-responsive materials. In this work, the first light-fueled supramolecular LCEs suitable for the direct ink writing (DIW) of soft actuators are synthesized in which a photopolymerization step is not needed. With the responsive supramolecular material, 3D-printed objects are fabricated by exploiting the thermoreversible interplay of the hydrogen-bonding physical cross-links. After printing, the supramolecular LCE shows reversible shape changes in response to light and is capable of bending and lifting a load. Through the combined photothermal and photochemical contributions of the incorporated azobenzene, the actuators can be triggered both in air and water. The freedom provided by DIW allows for the printing of complex responsive objects, as demonstrated by fabricating re-entrant honeycomb and spiral director structures. This approach of printing light-responsive supramolecular soft actuators opens avenues toward the application of “smart” and sustainable materials for additive manufacturing without the requirement of photo-crosslinking.

Recent years have seen major advances in the additive manufacturing of stimuli-responsive materials, also known as “4D printing,” among which liquid crystal elastomers (LCEs) play an important role. However, during fabrication photo-crosslinking of the LCEs is required, but this step is time-consuming and efficient polymerization is challenging, especially in the case of light-responsive materials. In this work, the first light-fueled supramolecular LCEs suitable for the direct ink writing (DIW) of soft actuators are synthesized in which a photopolymerization step is not needed. With the responsive supramolecular material, 3D-printed objects are fabricated by exploiting the thermoreversible interplay of the hydrogen-bonding physical cross-links. After printing, the supramolecular LCE shows reversible shape changes in response to light and is capable of bending and lifting a load. Through the combined photothermal and photochemical contributions of the incorporated azobenzene, the actuators can be triggered both in air and water. The freedom provided by DIW allows for the printing of complex responsive objects, as demonstrated by fabricating re-entrant honeycomb and spiral director structures. This approach of printing light-responsive supramolecular soft actuators opens avenues toward the application of “smart” and sustainable materials for additive manufacturing without the requirement of photo-crosslinking.

From the first experiments with biomaterials to mimic tissue properties, the mechanical and biochemical characterization has evolved extensively. Several properties can be described, however, what should be essential is to conduct a proper and physiologically relevant characterization. Herein, the influence of the reaction media (RM) and swelling media (SM)-phosphate buffered saline (PBS) and Dulbecco's modified Eagle's medium (DMEM) with two different glucose concentrations-is described in gelatin methacrylamide (GelMA) hydrogel mechanics and in the biological behavior of two tumoral cell lines (Caco-2 and HCT-116). All scaffolds are UV-photocrosslinked under identical conditions and evaluated for mass swelling ratio and stiffness. The results indicate that stiffness is highly susceptible to the RM, but not to the SM. Additionally, PBS-prepared hydrogels exhibited a higher photopolymerization degree according to high resolution magic-angle spinning (HR-MAS) NMR. These findings correlate with the biological response of Caco-2 and HCT-116 cells seeded on the substrates, which demonstrated flatter morphologies on stiffer hydrogels. Overall, cell viability and proliferation are excellent for both cell lines, and Caco-2 cells displayed a characteristic apical-basal polarization based on F-actin/Nuclei fluorescence images. These characterization experiments highlight the importance of conducting mechanical testing of biomaterials in the same medium as cell culture.

Soft and mechanically responsive actuators hold the promise to revolutionize the design and manufacturing of devices in the areas of microfluidics, soft robotics and biomedical engineering. In many of these applications, the actuators need to operate in a wet environment that can strongly affect their performance. In this paper, we report on the photomechanical response in a biological buffer of azobenzene-containing liquid crystal elastomer (LCE)-based actuators, prepared by four-dimensional (4D) printing. Although the photothermal contribution to the photoresponse is largely cancelled by the heat withdrawing capacity of the employed buffer, a significant photoinduced reversible contraction, in the range of 7% of its initial length, has been achieved under load, taking just a few seconds to reach half of the maximum contraction. Effective photomechanical work performance under physiological conditions has, therefore, been demonstrated in the 4D-printed actuators. Advantageously, the photomechanical response is not sensitive to salts present in the buffer differently to hydrogels with responses highly dependent on the fluid composition. Our work highlights the capabilities of photomechanical actuators, created using 4D printing, when operating under physiological conditions, thus showing their potential for application in the microfluidics and biomedical fields.

Recently, significant advances have been achieved to precisely program the response of liquid crystal elastomers (LCEs) through extrusion-based additive manufacturing techniques; however, important challenges remain, especially when well-defined scaffolds based on ultrafine fibers are required. Here the melt electrowriting of reactive liquid crystalline inks, leading, after ultraviolet-light-induced crosslinking, to digitally positioned uniform LCE fibers with diameters ranging from hundreds of nanometers to tens of micrometers is presented, which is hardly accessible with conventional extrusion-based printing techniques. The electrowriting process induces the preferential alignment of the mesogens parallel to the fiber's axis. Such an alignment, defined by the printing path, determines the mechanical response of the crosslinked material upon stimulation. This manufacturing platform allows the preparation of open square lattice scaffolds with ultrafine fibers (a few micrometers in diameter), periods as small as 90 µm, and well-defined morphology. Additionally, the combination of accurate fiber stacking (up to 50 layers) and fiber fusion between layers leads to unprecedented microstructures composed of high-aspect-ratio LCE thin walls. The possibility of digitally controlling the printing of fibers allows the preparation complex fiber-based scaffolds with programmed and reversible shape-morphing, thus opening new avenues to prepare miniaturized actuators and smart structures for soft robotics and biomedical applications.

The tissue microenvironment plays a crucial role in tissue homeostasis and disease progression. However, the in vitro simulation has been limited by the lack of adequate biomimetic models in the last decades. Thanks to the advent of microfluidic technology for cell culture applications, these complex microenvironments can be recreated by combining hydrogels, cells and microfluidic devices. Nevertheless, this advance has several limitations. When cultured in three-dimensional (3D) hydrogels inside microfluidic devices, contractile cells may exert forces that eventually collapse the 3D structure. Disrupting the compartmentalisation creates an obstacle to long-term or highly cell-concentrated assays, which are extremely relevant for multiple applications such as fibrosis or ischaemia. Therefore, we tested surface treatments on cyclic-olefin polymer-based microfluidic devices (COP-MD) to promote the immobilisation of collagen as a 3D matrix protein. Thus, we compared three surface treatments in COP devices for culturing human cardiac fibroblasts (HCF) embedded in collagen hydrogels. We determined the immobilisation efficiency of collagen hydrogel by quantifying the hydrogel transversal area within the devices at the studied time points. Altogether, our results indicated that surface modification with polyacrylic acid photografting (PAA-PG) of COP-MD is the most effective treatment to avoid the quick collapse of collagen hydrogels. As a proof-of-concept experiment, and taking advantage of the low-gas permeability properties of COP-MD, we studied the application of PAA-PG pre-treatment to generate a self-induced ischaemia model. Different necrotic core sizes were developed depending on initial HCF density seeding with no noticeable gel collapse. We conclude that PAA-PG allows long-term culture, gradient generation and necrotic core formation of contractile cell types such as myofibroblasts. This novel approach will pave the way for new relevant in vitro co-culture models

Pick-and-place operations for transporting objects precisely to a target position are a prominent function of (soft-) robotic systems. Therefore, there is great interest in industry to improve the characteristic gripping, holding, and releasing methods involved in pick-and-place operations. Within living organisms such as octopi, nature demonstrates that multiple types of conjointly working actuators are required for flexible pick-and-place operations. Herein, a multifunctional soft robotic arm is developed, capable of transporting an object within 3D space. The soft robotic arm consists of two structural actuators (rotating base and lifting unit) and a suction cup-based gripper. The structural actuator acts as both the load bearing and actuating components of the robotic system. Yet, the gripper is the crucial innovation within the robotic arm. A cephalopod-limb-inspired gripper functioning through the reversible flat-to-conical deformation of azimuthally aligned liquid crystal elastomer (LCE) films is proposed. The pressure-generating actuation mechanism of the gripper means that no external device is needed to operate the gripping function. Akin to natural systems, the in-tandem operation of the actuators in the soft robotic arm allows for multifactored tasks. Yet, the design achieves this through the use of a single material, which is not innate in natural archetypes.

Pick-and-place operations for transporting objects precisely to a target position are a prominent function of (soft-) robotic systems. Therefore, there is great interest in industry to improve the characteristic gripping, holding, and releasing methods involved in pick-and-place operations. Within living organisms such as octopi, nature demonstrates that multiple types of conjointly working actuators are required for flexible pick-and-place operations. Herein, a multifunctional soft robotic arm is developed, capable of transporting an object within 3D space. The soft robotic arm consists of two structural actuators (rotating base and lifting unit) and a suction cup-based gripper. The structural actuator acts as both the load bearing and actuating components of the robotic system. Yet, the gripper is the crucial innovation within the robotic arm. A cephalopod-limb-inspired gripper functioning through the reversible flat-to-conical deformation of azimuthally aligned liquid crystal elastomer (LCE) films is proposed. The pressure-generating actuation mechanism of the gripper means that no external device is needed to operate the gripping function. Akin to natural systems, the in-tandem operation of the actuators in the soft robotic arm allows for multifactored tasks. Yet, the design achieves this through the use of a single material, which is not innate in natural archetypes.

Optical planar waveguide sensors, able to detect and process information from the environment in a fast, cost-effective, and remote fashion, are of great interest currently in different application areas including security, metrology, automotive, aerospace, consumer electronics, energy, environment, or health. Integration of networks of these systems together with other optical elements, such as light sources, readout, or detection systems, in a planar waveguide geometry is greatly demanded towards more compact, portable, and versatile sensing platforms. Herein, we report an optical temperature sensor with a planar waveguide architecture integrating inkjet-printed luminescent light coupling-in and readout elements with matched emission and excitation. The first luminescent element, when illuminated with light in its absorption band, emits light that is partially coupled into the propagation modes of the planar waveguide. Remote excitation of this element can be performed without the need for special alignment of the light source. A thermoresponsive liquid crystal-based film regulates the amount of light coupled out from the planar waveguide at the sensing location. The second luminescent element partly absorbs the waveguided light that reaches its location and emits at longer wavelengths, serving as a temperature readout element through luminescence intensity measurements. Overall, the ability of inkjet technology to digitally print luminescent elements demonstrates great potential for the integration and miniaturization of light coupling-in and readout elements in optical planar waveguide sensing platforms.

Photoembossing is a powerful photolithographic technique to prepare surface relief structures relying on polymerization-induced diffusion in a solventless development step. Conveniently, surface patterns are formed by two or more interfering laser beams without the need for a litho-graphic mask. The use of nanosecond pulsed light-based interference lithography strengthens the pattern resolution through the absence of vibrational line pattern distortions. Typically, a conventional photoembossing protocol consists of an exposure step at room temperature that is followed by a thermal development step at high temperature. In this work, we explore the possibility to perform the pulsed holographic exposure directly at the development temperature. The surface relief structures generated using this modified photoembossing protocol are compared with those generated using the conventional one. Importantly, the enhancement of surface relief height has been observed by exposing the samples directly at the development temperature, reaching approximately double relief heights when compared to samples obtained using the conventional protocol. Advanta-geously, the light dose needed to reach the optimum height and the amount of photoinitiator can be substantially reduced in this modified protocol, demonstrating it to be a more efficient process for surface relief generation in photopolymers. Kidney epithelial cell alignment studies on substrates with relief-height optimized structures generated using the two described protocols demonstrate improved cell alignment in samples generated with exposure directly at the development tempera-ture, highlighting the relevance of the height enhancement reached by this method. Although cell alignment is well-known to be enhanced by increasing the relief height of the polymeric grating, our work demonstrates nano-second laser interference photoembossing as a powerful tool to easily prepare polymeric gratings with tunable topography in the rang

[ES] La presente invención se refiere a un procedimiento de fabricación de una válvula microfluídica, que comprende: disponer un sustrato (1) que comprende al menos un material mecánicamente inerte a una o más propiedades físico-químicas en el tiempo; e imprimir sobre el sustrato (1), mediante fabricación aditiva, una disposición de uno o más filamentos (2) de un material con respuesta mecánica a una o más de dichas propiedades físico-químicas en el tiempo. El sustrato (1) de material inerte y los filamentos (2) de material con respuesta mecánica configuran un volumen (3) de paso de un fluido a través de la válvula, donde la sucesión de filamentos (2) del material con respuesta mecánica se dispone de forma que la variación de uno o más de los parámetros físico-químicos induce una alteración en el orden molecular del LCP, contrayendo o expandiendo sus cadenas poliméricas a lo largo de una dirección longitudinal o transversal de los filamentos (2), y conduciendo a la reducción o al aumento del volumen (3) de paso de fluido., [EN] The present invention refers to a method of manufacturing a microfluidic valve, comprising: providing a substrate (1) comprising at least one material that is mechanically inert to one or more physicochemical properties over time; and printing on the substrate (1), by additive manufacturing, an arrangement of one or more filaments (2) of a material with mechanical response to one or more of said physicochemical properties over time. The substrate (1) of inert material and the filaments (2) of material with mechanical response configure a volume (3) of passage of a fluid through the valve, where the succession of filaments (2) of material with mechanical response is It has such a way that the variation of one or more of the physicochemical parameters induces an alteration in the molecular order of the LCP, contracting or expanding its polymeric chains along a longitudinal or transverse direction of the filaments (2), and leading to the reduction or to the increase of the volume (3) of passage of fluid.