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Liquid crystalline (LC) materials are especially suited for the preparation of active three-dimensional (3D) and 4D microstructures using two-photon laser printing. To achieve the desired actuation, the alignment of the LCs has to be controlled during the printing process. In most cases studied before, the alignment relied on surface modifications and complex alignment patterns and concomitant actuation were not possible. Here, we introduce a strategy for spatially aligning LC domains in three-dimensional space by using 3D-printed polydimethylsiloxane-based microscaffolds as confinement barriers, which induce the desired director field. The director field resulting from the boundary conditions is calculated with Landau de Gennes theory and validated by comparing experimentally measured and theoretically predicted birefringence patterns. We demonstrate our procedures for structures of varying complexity and then employed them to fabricate 4D microstructures that show the desired actuation. Overall, we obtain excellent agreement between theory and experiment. This opens the door for rational design of functional materials for 4D (micro)printing in the future.

Iron gall ink (IGI), renowned for its indelibility, was the most important writing ink in the Western world from the 15th to the late 19th century. However, it is now known that IGIs induce acid-catalyzed hydrolysis and iron-catalyzed oxidation of the cellulose in historical paper documents. These mechanisms of deterioration cause significant damage to the writing support materials, including color alteration and burn-through appearance, and in the worst scenarios, physical disintegration of the supports. Minimally invasive, long-term effective conservation treatments that tackle the underlying mechanisms of IGI degradation and their corrosion effects are yet to be developed. This study introduces the deployment of hydrophobic and anticorrosive polyoxometalate-ionic liquids (POM-ILs) as colorless coatings to counteract IGI-corrosion of cellulosic supports. Model IGI-containing papers (mockups) were prepared, coated with POM-ILs, and artificially aged to assess the compatibility of POM-ILs with IGI-containing documents. Comprehensive monitoring using colorimetric and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM/EDS) analyses showed minimal interference with the aesthetic properties and morphology of the IGI mockups. In addition, polyoxometalates (POMs) with vacant metal atom sites in the cluster shell can be used to coordinate free transition metal ions. The ability of a monolacunary Keggin-type polyoxotungstate to coordinate free Fe(II) from IGI solution was demonstrated using UV-vis analysis. This led to the formation of a dimeric species, [(SiW 11 O 39 Fe) 2 O]K 12 ·28H 2 O, which was characterized by single-crystal X-ray diffraction. Altogether, this study points to POM-ILs as promising protective coatings for effectively preserving historical IGI-written heritage., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

This study investigates the activity of novel gold(I) and copper(I)/zinc(II) heteronuclear complexes against colon cancer. The synthesised heteronuclear Au(I)-Cu(I) and Au(I)-Zn(II) complexes were characterised and evaluated for their anticancer activity using human colon cancer cell lines (Caco-2). The complexes exhibited potent cytotoxicity, with IC 50 values in the low micromolar range, and effectively induced apoptosis in cancer cells. In the case of complex [Cu{Au(Spy)(PTA)} 2 ]PF 6 ( 2 ), its cytotoxicity is ×10 higher than its mononuclear precursor, while showing low cytotoxicity towards differentiated healthy cells. Mechanistic studies revealed that complex 2 inhibits the activity of thioredoxin reductase, a key enzyme involved in redox regulation, leading to an increase in reactive oxygen species (ROS) levels and oxidative stress, in addition to an alteration in DNA's tertiary structure. Furthermore, the complexes demonstrated a strong binding affinity to bovine serum albumin (BSA), suggesting the potential for effective drug delivery and bioavailability. Collectively, these findings highlight the potential of the investigated heteronuclear Au(I)-Cu(I) and Au(I)-Zn(II) complexes as promising anticancer agents, particularly against colon cancer, through their ability to disrupt redox homeostasis and induce oxidative stress-mediated cell death.

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., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Microalgae have emerged as sustainable feedstocks due to their ability to fix CO 2 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. This work presents the use of microalgae as "biofactories" to generate materials that can be further 3D printed in high resolution. Two taxonomically different strains -Odontella aurita (O. aurita, BEA0921B) and Tetraselmis striata (T. striata, BEA1102B)- are identified as suitable microalgae for this purpose. The extracts obtained from the microalgae (mainly triglycerides with chlorophyll derivatives) are 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. These findings open new possibilities for the next generation of sustainable, biobased, and biocompatible materials with great potential in life science applications., (© 2024 Wiley‐VCH GmbH.)

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., (© 2024 Wiley‐VCH GmbH.)

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., (© 2024 Wiley‐VCH GmbH.)

Neurons are plastic. That is, they change their activity according to different behavioural conditions. This endows pyramidal neurons with an incredible computational power for the integration and processing of synaptic inputs. Plasticity can be investigated at different levels of investigation within a single neuron, from spines to dendrites, to synaptic input. Although most of our knowledge stems from the in vitro brain slice preparation, plasticity plays a vital role during behaviour by providing a flexible substrate for the execution of appropriate actions in our ever-changing environment. Owing to advances in recording techniques, the plasticity of neurons and the neural networks in which they are embedded is now beginning to be realized in the in vivo intact brain. This review focuses on the structural and functional synaptic plasticity of pyramidal neurons , with a specific focus on the latest developments from in vivo studies. This article is part of a discussion meeting issue 'Long-term potentiation: 50 years on'.

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., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

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.

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., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

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., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

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 ZrO 2 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., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Although the Na-K-Cl cotransporter (NKCC1) inhibitor bumetanide has prominent positive effects on the pathophysiology of many neurological disorders, the mechanism of action is obscure. Attention paid to elucidating the role of Nkcc1 has mainly been focused on neurons, but recent single cell mRNA sequencing analysis has demonstrated that the major cellular populations expressing NKCC1 in the cortex are non-neuronal. We used a combination of conditional transgenic animals, in vivo electrophysiology, two-photon imaging, cognitive behavioural tests and flow cytometry to investigate the role of Nkcc1 inhibition by bumetanide in a mouse model of controlled cortical impact (CCI). Here, we found that bumetanide rescues parvalbumin-positive interneurons by increasing interneuron-microglia contacts shortly after injury. The longitudinal phenotypic changes in microglia were significantly modified by bumetanide, including an increase in the expression of microglial-derived BDNF. These effects were accompanied by the prevention of CCI-induced decrease in hippocampal neurogenesis. Treatment with bumetanide during the first week post-CCI resulted in significant recovery of working and episodic memory as well as changes in theta band oscillations 1 month later. These results disclose a novel mechanism for the neuroprotective action of bumetanide mediated by an acceleration of microglial activation dynamics that leads to an increase in parvalbumin interneuron survival following CCI, possibly resulting from increased microglial BDNF expression and contact with interneurons. Salvage of interneurons may normalize ambient GABA, resulting in the preservation of adult neurogenesis processes as well as contributing to bumetanide-mediated improvement of cognitive performance., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Guarantors of Brain.)

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., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

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 F 4 TCNQ 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.

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., (© 2023. Springer Nature Limited.)

New gold(I) complexes with coordination to 5-fluorouracil (5-FU), an anticancer drug with antibacterial properties, have been synthesised and characterised, and are the first reported examples of 5-FU-Au compounds. These new complexes show high solution stability, even in the presence of a cysteine derivative, and so were evaluated as antibacterial compounds against model Gram-positive and Gram-negative bacteria. All the complexes show excellent antibacterial activity against Gram-positive B. subtilis , most of them improving the activity of 5-FU alone. Furthermore, these new complexes are also active against Gram-negative E. coli , where [Au(5-FU)(PTA)], the complex with the smallest phosphane, is the most bactericidal, 32 times more active than 5-FU on its own.

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., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Alzheimer's disease (AD) is an incurable neurodegenerative disease that leads to the progressive and irreversible loss of mental functions. The amyloid beta (Aβ) peptide involved in the disease is responsible for the production of damaging reactive oxygen species (ROS) when bound to Cu ions. A therapeutic approach that consists of removing Cu ions from Aβ to alter this deleterious interaction is currently being developed. In this context, we report the ability of five different 12-membered thiaazacyclen ligands to capture Cu from Aβ and to redox silence it. We propose that the presence of a sole sulfur atom in the ligand increases the rate of Cu capture and removal from Aβ, while the kinetic aspect of the chelation was an issue encountered with the 4N parent ligand. The best ligand for removing Cu from Aβ and inhibiting the associated ROS production is the 1-thia-4,7,10-triazacyclododecane [3N1S]. Indeed the replacement of more N by S atoms makes the corresponding Cu complexes easier to reduce and thus able to produce ROS on their own. In addition, the ligand with three sulfur atoms has a weaker affinity for Cu II than Aβ, and is thus unable to remove Cu from CuAβ., (© 2023 Wiley-VCH GmbH.)

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., (© 2023. The Author(s).)

Ongoing neurogenesis in the dentate gyrus (DG) subregion of the hippocampus results in a heterogenous population of neurons. Immature adult-born neurons (ABNs) have physiological and anatomical properties that may give them a unique role in learning. For example, compared to older granule neurons, they have greater somatic excitability, which could facilitate their recruitment into memory traces. However, recruitment is also likely to depend on interactions with other DG neurons through processes such as lateral inhibition. Immature ABNs target inhibitory interneurons and, compared to older neurons, they receive less GABAergic inhibition. Thus, they may induce lateral inhibition of mature DG neurons while being less susceptible to inhibition themselves. To test this we used a chemogenetic approach to silence immature ABNs as rats learned a spatial water maze task, and measured activity (Fos expression) in ABNs and developmentally-born neurons (DBNs). A retrovirus expressing the inhibitory DREADD receptor, hM4Di, was injected into the dorsal DG of male rats at 6w to infect neurons born in adulthood. Animals were also injected with BrdU to label DBNs or ABNs. DBNs were significantly more active than immature 4-week-old ABNs. Silencing 4-week-old ABNs did not alter learning but it increased activity in DBNs. However, silencing ABNs did not affect activation in other ABNs within the DG. Silencing ABNs also did not alter Fos expression in parvalbumin- and somatostatin-expressing interneurons. Collectively, these results suggest that ABNs may directly inhibit DBN activity during hippocampal-dependent learning, which may be relevant for maintaining sparse hippocampal representations of experienced events., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Organo-functionalisation of polyoxometalates (POMs) represents an effective approach to obtain diverse arrays of functional structures and materials, where the introduction of organic moieties into the POM molecules can dramatically change their surface chemistry, charge, polarity, and redox properties. The synergistic combination of POMs and peptides, which perform a myriad of essential roles within cellular biochemistry, including protection and transport in living organisms, leads to functional hybrid materials with unique properties. In this Perspective article, we present the principal synthetic routes to prepare and characterise POM-peptide hybrids, together with a comprehensive description of how their properties - such as redox chemistry, stereochemistry and supramolecular self-assembly - give rise to materials with relevant catalytic, adhesive, and biomedical applications. By presenting the state-of-the-art of the POM-peptide field, we show specifically how emerging chemical approaches can be harnessed to develop tailored POM-peptide materials with synergistic properties for applications in a variety of disciplines., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this paper we describe the synthesis of new N -heterocyclic carbene (NHC) gold(I) derivatives with flavone-derived ligands with a propargyl ether group. The compounds were screened for their antimicrobial and anticancer activities, showing greater activity against bacteria than against colon cancer cells (Caco-2). Complexes [Au(L2b)(IMe)] ( 1b ) and [Au(L2b)(IPr)] ( 2b ) were found to be active against both Gram-positive and Gram-negative strains. The mechanism of action of 1b was evaluated by measurement of thioredoxin reductase (TrxR) and dihydrofolate reductase (DHFR) activity, besides scanning electron microscopy (SEM). Inhibition of the enzyme thioredoxin reductase is not observed in either Escherichia Coli or Caco-2 cells; however, DHFR activity is compromised after incubation of E. coli cells with complex 1b . Moreover, loss of structural integrity and change in bacterial shape is observed in the images obtained from scanning electron microscopy (SEM) after treatment E. coli cells with complex 1b .

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 (Col h ) 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 Col h 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 Col h LC should open new opportunities for the fabrication of functional porous microdevices with potential application in catalysis, filtration, separation, or molecular recognition.

The increasing resistance of pathogenic microorganisms against common treatments requires innovative concepts to prevent infection and avoid long-term microbe viability on commonly used surfaces. Here, we report the preparation of a hybrid antimicrobial material based on the combination of microbiocidal polyoxometalate-ionic liquids (POM-ILs) and a biocompatible polymeric support, which enables the development of surface coatings that prevent microbial adhesion. The composite material is based on an antibacterial and antifungal room-temperature POM-IL composed of guanidinium cations ( N , N , N ', N '-tetramethyl- N ″, N ″-dioctylguanidinum) combined with lacunary Keggin-type polyoxotungstate anions, [α-SiW 11 O 39 ] 8- . Integration of the antimicrobial POM-IL into the biocompatible, flexible, and stable polymer poly(methyl methacrylate) (PMMA) results in processable films, which are suitable as surface coatings or packaging materials to limit the proliferation and spread of pathogenic microorganisms ( e.g. , on public transport and hospital surfaces, or in ready-to-eat-food packaging)., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

From swimming to walking and flying, animals have evolved specific locomotor strategies to thrive in different habitats. All types of locomotion depend on the integration of motor commands and sensory information to generate precisely coordinated movements. Cerebrospinal-fluid-contacting neurons (CSF-cN) constitute a vertebrate sensory system that monitors CSF composition and flow. In fish, CSF-cN modulate swimming activity in response to changes in pH and bending of the spinal cord; however, their role in mammals remains unknown. We used mouse genetics to study their function in quadrupedal locomotion. We found that CSF-cN are directly integrated into spinal motor circuits. The perturbation of CSF-cN function does not affect general motor activity nor the generation of locomotor rhythm and pattern but results in specific defects in skilled movements. These results identify a role for mouse CSF-cN in adaptive motor control and indicate that this sensory system evolved a novel function to accommodate the biomechanical requirements of limb-based locomotion., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Developing artificial metalloenzymes that possess a superior performance to their natural counterparts is an attractive concept. Polyoxometalates (POMs) are a class of anionic molecular metal-oxides with excellent redox properties and bioactivity. We have recently introduced "POMlymers" - covalently conjugated POM-peptide hybrid materials - where the polypeptide chain is obtained through a ring-opening polymerisation (ROP) of α-amino acid N -carboxyanhydrides (NCA) on an inorganic POM scaffold. Attracted by the idea of preparing artificial metalloenzymes, here we report the supramolecular self-assembly of POMlymer hybrids into nanoparticles where an optimal environment for catalysis is created. Our results demonstrate that the self-assembly of covalent POMlymers, enhances the peroxidase-like activity of the parent POM anion whereas, in contrast, the catalytic activity for nanoparticles obtained by ionic self-assembly of the same peptide and POM components practically disappears. Furthermore, POMlymer nanoparticles also present antimicrobial and antibiofilm activity against the skin bacterium Staphylococcus epidermidis ; whereas, ionic POM-peptide hybrids significantly increase biofilm production and endogenous production of reactive oxygen species. In summary, we present the self-assembly of POMlymer hybrids into nanoparticles and a combination of peroxidase activity and microbiology assays that show that the POM-peptide covalent bond is essential for the stability of the self-assembled nanoparticles and therefore for their catalytic and biological activity.

Two Keggin polyoxometalates were used as new copper ligands to counteract the effects of Cu II (Amyloid-β) interaction. Their ability to remove Cu II from Cu II (Amyloid-β), to stop Cu II (Amyloid-β) induced formation of reactive oxygen species and to restore apo-like self-assembly of Cu II (Amyloid-β) was shown.

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.