Search

Abstract Two‐photon lithography (TPL) is a powerful technique for creating 3D microarchitectures. Applied to high‐refractive‐index materials like ZrO2, it promises advanced optics. This is the case of ZrO2 host matrixes in combination with luminescent dopants. However, due to the nonideal crystallinity attained to the TPL pre‐ceramic replica from a custom‐made photoresin, the emission of lanthanide (Ln) dopants in ZrO2 microarchitectures can be suboptimal. However, crystallinity exacerbated by annealing can promote Ln‐emission, thereby enabling the integration of ceramic micro‐optic into a low‐temperature process. This work presents a photoresin containing a metal‐organic monomer tailored for TPL, enabling the fabrication of Ln‐doped tetragonal ZrO2 (t‐ZrO2) microarchitectures. The emission properties of Ln‐doped microarchitectures with trivalent Ln ions (Ln3+), i.e., Yb3+ (2.5 mol%), Er3+ (0.35 mol%), and Tm3+ (0.35 mol%) are studied. The results demonstrate that Ln emission is absent when annealing the microarchitectures at 600 °C. Annealing at 750 °C activates Ln3+ emissions, including 2F5/2–2F7/2 (infrared), 4S3/2–4I15/2 (green), and 3H4–3F6 (near‐infrared) transitions corresponding to Yb, Er, and Tm species. Transmission electron microscopy (TEM) confirms that t‐ZrO2 crystallinity becomes more prominent at 750 °C, demonstrating the promotion of Ln emissions upon thermal treatment and underscoring the role of crystalline in TPL micro‐optical ceramics.

Abstract Intravascular surgical instruments require precise navigation within narrow vessels, necessitating maximum flexibility, minimal diameter, and high degrees of freedom. Existing tools often lack control during insertion due to undesirable bending, limiting vessel accessibility and risking tissue damage. Next-generation instruments aim to develop hemocompatible untethered devices controlled by external magnetic forces. Achieving this goal remains complex due to testing and implementation challenges in clinical environments. Here we assess the operational effectiveness of hemocompatible untethered magnetic robots using an ex vivo porcine aorta model. The results demonstrate a linear decrease in the swimming speed of untethered magnetic robots as arterial blood flow increases, with the capability to navigate against a maximum arterial flow rate of 67 mL/min. The untethered magnetic robots effectively demonstrate locomotion in a difficult-to-access target site, navigating through the abdominal aorta and reaching the distal end of the renal artery.

This paper reports on the design of an innovative Electrochemistry course, part of a Chemical Science Engineering programme. Teachers have observed that their students' understanding of electrochemical concepts and phenomena is insufficient to attempt connections to further concepts, and to generate new knowledge in scientific problem-solving. A new course was required aiming to contribute to students' building mastery of concepts and deep insight into phenomena, both in and beyond the learning context. The course was designed tapping on ideas of inquiry-based learning and involving of conceptual modelling as a scaffold to learning. This pedagogical intervention departs from the consideration that conceptual modelling is an essential reasoning ability of (engineering) scientists and, consistently, it constitutes a key learning objective. Concurrent with the implementation of this course, an accompanying empirical investigation was set up to grasp how students learn electrochemistry with this novel pedagogical approach, and whether (and to what extent) there is any observable effect on the learning and transfer of electrochemical concepts. Both the instructional design of the course and the educational research design integrate considerations from Chemical Science, Philosophy of Science in Practice, and Education Sciences. The implications for engineering education and for educational research are discussed.

The additive manufacturing (AM) of yttria-stabilized zirconia (YSZ) microarchitectures with sub-micrometer precision via two-photon lithography (TPL), utilizing custom photoresin containing zirconium and yttrium monomers is investigated. YSZ 3D microarchitectures can be formed at low temperatures (600 °C). The low-temperature phase stabilization of ZrO2 doped with Y2O3 demonstrates that doping ZrO2 with ≈ 10 mol% Y2O3 stabilizes the c-ZrO2 phase. The approach does not utilize YSZ particles as additives. Instead, the crystallization of the YSZ phase is initiated after printing, i.e., during thermal processing in the air at 600 °C – 1200 °C for one and two hours. The YSZ microarchitectures are characterized in detail. This includes understanding the role of defect chemistry, which has been overlooked in TPL-enabled micro-ceramics. Upon UV excitation, defect-related yellowish-green emission is observed from YSZ microarchitectures associated with intrinsic and extrinsic centers, correlated with the charge compensation due to Y3+ doping. The mechanical properties of the microarchitectures are assessed with manufactured micropillars. Micropillar compression yields the intrinsic mechanical strength of YSZ. The highest strength is observed for micropillars annealed at 600 °C, and this characteristic decreased with an increase in the annealing temperature. The deformation behavior gradually changes from ductile to brittle-like, correlating with the Hall–Petch strengthening mechanism.

In vitro cellular models denote a crucial part of drug discovery programs as they aid in identifying successful drug candidates based on their initial efficacy and potency. While tremendous headway has been achieved in improving 2D and 3D culture techniques, there is still a need for physiologically relevant systems that can mimic or alter cellular responses without the addition of external biochemical stimuli. A way forward to alter cellular responses is using physical cues, like 3D topographical inorganic substrates, to differentiate macrophage-like cells. Herein, protein secretion and gene expression markers for various macrophage subsets cultivated on a 3D topographical substrate are investigated. The results show that macrophages differentiate into anti-inflammatory M2-type macrophages, secreting increased IL-10 levels compared to the controls. Remarkably, these macrophage cells are differentiated into the M2d subset, making up the main component of tumour-associated macrophages (TAMs), as measured by upregulated Il-10 and Vegf mRNA. M2d subset differentiation is attributed to the topographical substrates with 3D fractal-like geometries arrayed over the surface, else primarily achieved by tumour-associated factors in vivo. From a broad perspective, this work paves the way for implementing 3D topographical inorganic surfaces for drug discovery programs, harnessing the advantages of in vitro assays without external stimulation and allowing the rapid characterisation of therapeutic modalities in physiologically relevant environments.

Two-photon lithography (TPL) is a promising technique for manufacturing ceramic microstructures with nanoscale resolution. The process relies on tailor-made precursor resins rich in metal–organic and organic constituents, which can lead to carbon-based residues incorporated within the ceramic microstructures. While these are generally considered unwanted impurities, our study reveals that the presence of carbon-rich residues in the form of graphitic and disordered carbon in tetragonal (t-) ZrO2 can benefit the mechanical strength of TPL microstructures. In order to achieve a better understanding of these effects, we deconvolute the structural and materials contributions to the strength of the 3D microarchitectures by comparing them to plain micropillars. We vary the organic content by different thermal treatments, resulting in different crystal structures. The highest compression strength of 3.73 ± 0.21 GPa and ductility are reached for the t-ZrO2 micropillars, which also contain the highest carbon content. This paradoxical finding opens up new perspectives and will foster the development of “brick and mortar”-like ceramic microarchitectures.

With the growing population, access to clean water is one of the 21st-century world’s challenges. For this reason, different strategies to reduce pollutants in water using renewable energy sources should be exploited. Photocatalysts with extended visible light harvesting are an interesting route to degrade harmful molecules utilized in plastics, as is the case of Bisphenol A (BPA). This work uses a microwave-assisted route for the synthesis of two photocatalysts (BiOI and Bi2MoO6). Then, BiOI/Bi2MoO6 heterostructures of varied ratios were produced using the same synthetic routes. The BiOI/Bi2MoO6 with a flower-like shape exhibited high photocatalytic activity for BPA degradation compared to the individual BiOI and Bi2MoO6. The high photocatalytic activity was attributed to the matching electronic band structures and the interfacial contact between BiOI and Bi2MoO6, which could enhance the separation of photo-generated charges. Electrochemical, optical, structural, and chemical characterization demonstrated that it forms a BiOI/Bi2MoO6 p-n heterojunction. The free radical scavenging studies showed that superoxide radicals (O2•−) and holes (h+) were the main reactive species, while hydroxyl radical (•OH) generation was negligible during the photocatalytic degradation of BPA. The results can potentiate the application of the microwave synthesis of photocatalytic materials.

Tailoring the properties of microfabricated ceramics through doping can unlock new avenues for the additive manufacturing (AM) of advanced 3D architectures. The first step to achieving optical functionality is to control material morphology, crystallinity, and defects associated with the composition of the produced AM architecture and dopants. For this purpose, AM of zinc‐doped zirconia (ZrO2:Zn) 3D microarchitectures is proposed using two‐photon lithography and tailor‐made resin. It is found that Zn doping modulates ZrO2:Zn architecture crystallinity and optical properties. The modification of optical properties through Zn doping is confirmed by micro‐photoluminescence, where higher energy photon emission is observed due to the promotion of oxygen vacancies and surface defects. It is also shown that Zn 2.5% and 5 wt% stabilizes the monoclinic ZrO2 at a lower temperature than in the case of undoped ZrO2. Furthermore, there is evidence that Zn tends to form ZnO wurtzite, which is later sublimated. The findings provide a promising route to understand the role of defects ZrO2:Zn optically upon annealing. [ABSTRACT FROM AUTHOR]

Surface engineering is a promising strategy to limit or prevent the formation of biofilms. The use of topographic cues to influence early stages of biofilm formationn has been explored, yet many fundamental questions remain unanswered. In this work, we develop a topological model supported by direct experimental evidence, which is able to explain the effect of local topography on the fate of bacterial micro-colonies of Staphylococcus spp. We demonstrate how topological memory at the single-cell level, characteristic of this genus of Gram-positive bacteria, can be exploited to influence the architecture of micro-colonies and the average number of surface anchoring points over nano-patterned surfaces, formed by vertically aligned silicon nanowire arrays that can be reliably produced on a commercial scale, providing an excellent platform to investigate the effect of topography on the early stages of Staphylococcus spp. colonisation. The surfaces are not intrinsically antimicrobial, yet they delivered a topography-based bacteriostatic effect and a significant disruption of the local morphology of micro-colonies at the surface. The insights from this work could open new avenues towards designed technologies for biofilm engineering and prevention, based on surface topography.

Three-dimensional (3D) complex in vitro cell systems are well suited to providing meaningful and translatable results in drug screening, toxicity measurements, and biological studies. Reliable complex gastrointestinal in vitro models as a testbed for oral drug administration and toxicity are very valuable in achieving predictive results for clinical trials and reducing animal testing. However, producing these models is time-consuming due to the lengthy differentiation of HT29 or other cells into mucus-producing goblet cells or other intestinal cell lineages. In the present work, HT29 cells were grown on an inorganic topographic surface decorated with a periodic pattern of micrometre-sized amorphous SiO2 structures for up to 35 days. HT29 cells on topographic surfaces were compared to undifferentiated HT29 in glucose-containing medium on glass or culture dish and with HT29 cells differentiated for 30 days in the presence of methotrexate (HT29-MTX). The cells were stained with Alcian blue for mucus, antibodies for mucus 2 (goblet cells), villin (enterocytes), lysozyme (Paneth cells), and FITC-labeled lectins to identify different cells, glycomic profiles, and cell features. We observed that HT29 cells on topographic surfaces showed more similarities with the differentiated HT29-MTX than with undifferentiated HT29. They formed islands of cell clusters, as observed for HT29-MTX. Already after 2 days, the first mucus secretion was shown by Alcian blue stain and FITC-wheat germ agglutinin. After 4–6 days, mucus was observed on the cell surface and in the intercellular space. The cell layer was undulated, and in 3D reconstruction, the cells showed a clear polarisation with a strong actin signal to one membrane. The lectins and the antibody-staining confirmed the heterogeneous composition of differentiated HT29 cells on topographic surfaces after 6–8 days, or after 6–8 days following MTX differentiation (30 days).

In vitro cell models play important roles as testbeds for toxicity studies, drug development, or as replacements in animal experiments. In particular, complex tumor models such as hepatocellular carcinoma (HCC) are needed to predict drug efficacy and facilitate translation into clinical practice. In this work, topographical features of amorphous silicon dioxide (SiO2) are fabricated and tested for cell culture of primary HCC cells and cell lines. The topographies vary from pyramids to octahedrons to structures named fractals, with increased hierarchy and organized in periodic arrays (square or Hexagonal). The pyramids were found to promote complex 2D/3D tissue formation from primary HCC cells. It was found that the 2D layer was mainly composed of cancer-associated fibroblasts (CAFs), while the 3D spheroids were composed of tumor cells enwrapped by a CAF layer. Compared with conventional protocols for 3D cultures, this novel approach mimics the 2D/3D complexity of the original tumor by invading CAFs and a microtumor. Topographies such as octahedrons and fractals exclude tumor cells and allow one-step isolation of CAFs even directly from tumor tissue of patients as the CAFs migrate into the structured substrate. Cell lines form spheroids within a short time. The presented inorganic topographical surfaces stimulate complex spheroid formation while avoiding additional biological scaffolds and allowing direct visualization on the substrate.

Abstract Photo-responsive antibacterial surfaces combining both on-demand photo-switchable activity and sustained biocidal release were prepared using sequential chemical grafting of nano-objects with different geometries and functions. The multi-layered coating developed incorporates a monolayer of near-infrared active silica-coated gold nanostars (GNS) decorated by silver nanoparticles (AgNP). This modular approach also enables us to unravel static and photo-activated contributions to the overall antibacterial performance of the surfaces, demonstrating a remarkable synergy between these two mechanisms. Complementary microbiological and imaging evaluations on both planktonic and surface-attached bacteria provided new insights on these distinct but cooperative effects.