Multi-responsive poly-catecholamine nanomembranes.

The contraction of nanomaterials triggered by stimuli can be harnessed for micro- and nanoscale energy harvesting, sensing, and artificial muscles toward manipulation and directional motion. The search for these materials is dictated by optimizing several factors, such as stimulus type, conversion efficiency, kinetics and dynamics, mechanical strength, compatibility with other materials, production cost and environmental impact. Here, we report the results of studies on bio-inspired nanomembranes made of poly-catecholamines such as polydopamine, polynorepinephrine, and polydextrodopa. Our findings reveal robust mechanical features and remarkable multi-responsive properties of these materials. In particular, their immediate contraction can be triggered globally by atmospheric moisture reduction and temperature rise and locally by laser or white light irradiation. For each scenario, the process is fully reversible, i.e., membranes spontaneously expand upon removing the stimulus. Our results unveil the universal multi-responsive nature of the considered polycatecholamine membranes, albeit with distinct differences in their mechanical features and response times to light stimulus. We attribute the light-triggered contraction to photothermal heating, leading to water desorption and subsequent contraction of the membranes. The combination of multi-responsiveness, mechanical robustness, remote control via light, low-cost and large-scale fabrication, biocompatibility, and low-environment impact makes polycatecholamine materials promising candidates for advancing technologies.

Spontaneous chiral symmetry breaking in polar fluid-heliconical ferroelectric nematic phase.

Spontaneous mirror symmetry breaking by formation of chiral structures from achiral building blocks and emergent polar order are phenomena rarely observed in fluids. Separately, they have both been found in certain nematic liquid crystalline phases; however, they have never been observed simultaneously. Here, we report a heliconical arrangement of achiral molecules in the ferroelectric nematic phase. The phase is thus spontaneously both polar and chiral. Notably, the pitch of the heliconical structure is comparable to the wavelength of visible light, giving selective reflection controllable by temperature or application of a weak electric field. Despite bearing resemblance to the heliconical twist-bend nematic phase, this chiral ferroelectric nematic phase arises from electrical interactions that induce a noncollinear orientation of electric dipoles.

Ion and Molecular Sieving With Ultrathin Polydopamine Nanomembranes.

In contrast to biological cell membranes, it is still a major challenge for synthetic membranes to efficiently separate ions and small molecules due to their similar sizes in the sub-nanometer range. Inspired by biological ion channels with their unique channel wall chemistry that facilitates ion sieving by ion-channel interactions, the first free-standing, ultrathin (10-17 nm) nanomembranes composed entirely of polydopamine (PDA) are reported here as ion and molecular sieves. These nanomembranes are obtained via an easily scalable electropolymerization strategy and provide nanochannels with various amine and phenolic hydroxyl groups that offer a favorable chemical environment for ion-channel electrostatic and hydrogen bond interactions. They exhibit remarkable selectivity for monovalent ions over multivalent ions and larger species with K+/Mg2+ of ≈4.2, K+/[Fe(CN)6]3- of ≈10.3, and K+/Rhodamine B of ≈273.0 in a pressure-driven process, as well as cyclic reversible pH-responsive gating properties. Infrared spectra reveal hydrogen bond formation between hydrated multivalent ions and PDA, which prevents the transport of multivalent ions and facilitates high selectivity. Chemically rich, free-standing, and pH-responsive PDA nanomembranes with specific interaction sites are proposed as customizable high-performance sieves for a wide range of challenging separation requirements.

Fast Photoactuation and Environmental Response of Humidity-Sensitive pDAP-Silicon Nanocantilevers.

Multi-responsive nanomembranes are a new class of advanced materials that can be harnessed in complex architectures for micro and nano-manipulators, artificial muscles, energy harvesting, soft robotics, and sensors. The design and fabrication of responsive membranes must meet such challenges as trade-offs between responsiveness and mechanical durability, volumetric low-cost production ensuring low environmental impact, and compatibility with standard technologies or biological systems This work demonstrates the fabrication of multi-responsive, mechanically robust poly(1,3-diaminopropane) (pDAP) nanomembranes and their application in fast photoactuators. The pDAP films are developed using a plasma-assisted polymerization technique that offers large-scale production and versatility of potential industrial relevance. The pDAP layers exhibit high elasticity with the Young's modulus of ≈7 GPa and remarkable mechanical durability across 20-80 °C temperatures. Notably, pDAP membranes reveal immediate and reversible contraction triggered by light, rising temperature, or reducing relative humidity underpinned by a reversible water sorption mechanism. These features enable the fabrication of photoactuators composed of pDAP-coated Si nanocantilevers, demonstrating ms timescale response to light, tens of µm deflections, and robust performance up to kHz frequencies. These results advance fundamental research on multi-responsive nanomembranes and hold the potential to boost versatile applications in light-to-motion conversion and sensing toward the industrial level.

Aluminium-Based Metal-Organic Framework Nano Cuboids and Nanoflakes with Embedded Gold Nanoparticles for Carbon Dioxide Fixation with Epoxides into Cyclic Esters.

The fixation of carbon dioxide with epoxides is one of the most attractive methods for the green utilisation of this greenhouse gas and leads to many valuable chemicals. This process is characterised by 100% atom efficiency; however, an efficient catalyst is required to achieve satisfactory yields. Metal-organic frameworks (MOFs) are recognised as being extremely promising for this purpose. Nevertheless, many of the proposed catalysts are based on ions of rare elements or elements not entirely safe for the environment; this is notable with commercially unavailable ligands. In an effort to develop novel catalysts for CO2 fixation on an industrial scale, we propose novel MOFs, which consist of aluminium ions coordinated with commercially available 1,4-naphthalene dicarboxylic acid (Al@NDC) and their nanocomposites with gold nanoparticles entrapped inside their structure (AlAu@NDC). Due to the application of 4-amino triazole and 5-amino tetrazole as crystallization mediators, the morphology of the synthesised materials can be modified. The introduction of gold nanoparticles (AuNPs) into the structure of the synthesised Al-based MOFs causes the change in morphology from nano cuboids to nanoflakes, simultaneously decreasing their porosity. However, the homogeneity of the nanostructures in the system is preserved. All synthesised MOF materials are highly crystalline, and the simulation of PXRD patterns suggests the same tetragonal crystallographic system for all fabricated nanomaterials. The fabricated materials are proven to be highly efficient catalysts for carbon dioxide cycloaddition with a series of model epoxides: epichlorohydrin; glycidol; styrene oxide; and propylene oxide. Applying the synthesised catalysts enables the reactions to be performed under mild conditions (90 °C; 1 MPa CO2) within a short time and with high conversion and yield (90% conversion of glycidol towards glycerol carbonate with 89% product yield within 2 h). The developed nanocatalysts can be easily separated from the reaction mixture and reused several times (both conversion and yield do not change after five cycles). The excellent performance of the fabricated catalytic materials might be explained by their high microporosity (from 421 m2 g-1 to 735 m2 g-1); many catalytic centres in the structure exhibit Lewis acids' behaviour, increased capacity for CO2 adsorption, and high stability. The presence of AuNPs in the synthesised nanocatalysts (0.8% w/w) enables the reaction to be performed with a higher yield within a shorter time; this is especially important for less-active epoxides such as propylene oxide (two times higher yield was obtained using a nanocomposite, in comparison with Al-MOF without nanoparticles).

Unrestricted Chiral Patterning by Laser Writing in Liquid Crystalline and Plasmonic Nanocomposite Thin Films.

Obtaining hierarchical structures with arbitrarily controlled chirality remains a challenge. Here, thin films featuring chiroptically bipolar patterns are produced by a device utilizing microscale photothermal re-melting of materials exhibiting chirality synchronization. This device operates autonomously, guided by an algorithm that facilitates the homochiral growth of supramolecular organic helices through controlling their re-melting. The chirality synchronization phenomena of constitutionally achiral molecules grants availability of both handednesses of the helices, enabling unrestricted chiral writing in the film. The collective chiroptical response of assembled molecules is utilised to guide the patterning process, creating a foundation for optically secured information. The established methodology enables achieving dissymmetry factor values for circular dichroism (CD) a magnitude higher than previously reported, as confirmed with state-of-the-art, synchrotron-based Mueller matrix polarimetry (MMP). Moreover, the developed method is extended to nanocomposites comprising gold nanoparticles, providing the opportunity to tune the CD toward the plasmonic region. This strategic application of photothermal processing, specifically laser-directed melting, uncovers the potential to broaden the selection of nanostructured materials with precisely designed functionalities for photonic applications.

Electrolyte Disturbances Related to Sodium and Potassium and Electroconvulsive Therapy: A Systematic Review.

INTRODUCTION: Electrolyte disturbances related to sodium and potassium affect patients with mental disorders undergoing electroconvulsive therapy (ECT). The objective of this study was to systematically summarize the data regarding ECT and electrolyte disturbances related to sodium and potassium. MATERIALS AND METHODS: A systematic literature review in accordance with PRISMA guidelines was conducted. Clinical studies of patients receiving ECT with electrolyte disturbances reported before or after treatment were included. RESULTS: We identified nine case reports and two retrospective studies describing electrolyte abnormalities occurring before or after ECT. ECT was effective and safe in patients with hyponatremia and hypernatremia, including the elderly patient population. This treatment was also effective in treating psychiatric symptoms that may persist after ionic equalization. Electrolyte disturbances after ECT were rare. Reports have suggested that succinylcholine used as a muscle relaxant was the main cause of hyperkalemia after ECT. CONCLUSIONS: Electrolyte control is a crucial aspect of guiding ECT therapy. In the context of sodium-related disorders, it is critical to control patient hydration as part of therapy. In addition, succinylcholine should not be used in patients with immobilization, such as catatonia or neuroleptic malignant syndrome. It is necessary to conduct further studies to clarify whether electrolyte concentration affects ECT parameters and clinical efficacy. In addition, it is necessary to assess the influence of various anesthetics on these conditions during ECT. The result of this review should be interpreted bearing in mind the small number of studies conducted to date and the low quality of the evidence they provide.

Block Copolymer-Templated, Single-Step Synthesis of Transition Metal Oxide Nanostructures for Sensing Applications.

The synthesis of transition metal oxide nanostructures, thanks to their high surface-to-volume ratio and the resulting large fraction of surface atoms with high catalytic activity, is of prime importance for the development of new sensors and catalytic materials. Here, we report an economical, time-efficient, and easily scalable method of fabricating nanowires composed of vanadium, chromium, manganese, iron, and cobalt oxides by employing simultaneous block copolymer (BCP) self-assembly and selective sequestration of metal-organic acetylacetonate complexes within one of the BCP blocks. We discuss the mechanism and the primary factors that are responsible for the sequestration and conformal replication of the BCP template by the inorganic material that is obtained after the polymer template is removed. X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (PXRD) studies indicate that the metal oxidation state in the nanowires produced by plasma ashing the BCP template closely matches that of the precursor complex and that their structure is amorphous, thus requiring high-temperature annealing in order to sinter them into a crystalline form. Finally, we demonstrate how the developed nanowire array fabrication scheme can be used to rapidly pattern a multilayered iron oxide nanomesh, which we then used to construct a prototype volatile organic compound sensor.

Secretory leukocyte protease inhibitor modulates FcεRI-dependent but not Mrgprb2-dependent mastocyte function in psoriasis.

Psoriasis, which involves mast cells, is a chronic inflammatory skin disorder whose pathophysiology is still not fully understood. We investigated the role of secretory leukocyte protease inhibitor (SLPI), a potential inhibitor of mastocyte serine proteases, on mast cell-dependent processes of relevance to the skin barrier defense in psoriasis. Here, we demonstrate that the dermal mast cells of patients with psoriasis express SLPI but not those of healthy donors. Moreover, SLPI transcripts were found to be markedly upregulated in murine mast cells by mediators derived from psoriasis skin explant cultures. Using mast cells from SLPI-deficient mice and their SLPI+ wild-type controls, we show that SLPI inhibits the activity of serine protease chymase in mastocytes. SLPI was also found to enhance the degranulation of mast cells activated via anti-IgE Abs but not Mrgprb2 ligands. Finally, we demonstrate that the expression and function of Mrgprb2 in mast cells are suppressed by a normal and, to a larger extent, psoriatic skin environment. Together, these findings reveal mechanisms underlying FcεRI- and Mrgprb2-dependent mast cell function that have not been described previously.

Ferroelectric Nematic-Isotropic Liquid Critical End Point.

A critical end point above which an isotropic phase continuously evolves into a polar (ferroelectric) nematic phase with an increasing electric field is found in a ferroelectric nematic liquid crystalline material. The critical end point is approximately 30 K above the zero-field transition temperature from the isotropic to nematic phase and at an electric field of the order of 10 V/µm. Such systems are interesting from the application point of view because a strong birefringence can be induced in a broad temperature range in an optically isotropic phase.

Perfect control for nonminimum-phase unstable systems defined in the multivariable continuous-time state-space framework - An inverse-based approach.

In this paper, a new perfect control law dedicated to nonminimum-phase unstable LTI MIMO systems governed in the continuous-time state-space domain is proposed. Two algorithms are investigated, one of which has turned out to be definitely accurate. Henceforth, the inverse model control-based formula can be applied to any right-invertible plants having more input than output variables. Last, not least, through the application of some generalized inverses, the perfect control procedure guarantees the structural stability behavior even for unstable systems. Thus, the notion of the nonminimum-phase property should be understood in terms of a possible achieveability covering the entire class of LTI MIMO continuous-time plants. Theoretical and practical simulation examples performed in the Matlab/Simulink environment confirm the feasibility of the newly introduced approach.

Autonomous x-ray scattering.

Autonomous experimentation (AE) is an emerging paradigm that seeks to automate the entire workflow of an experiment, including-crucially-the decision-making step. Beyond mere automation and efficiency, AE aims to liberate scientists to tackle more challenging and complex problems. We describe our recent progress in the application of this concept at synchrotron x-ray scattering beamlines. We automate the measurement instrument, data analysis, and decision-making, and couple them into an autonomous loop. We exploit Gaussian process modeling to compute a surrogate model and associated uncertainty for the experimental problem, and define an objective function exploiting these. We provide example applications of AE to x-ray scattering, including imaging of samples, exploration of physical spaces through combinatorial methods, and coupling toin situprocessing platforms These uses demonstrate how autonomous x-ray scattering can enhance efficiency, and discover new materials.

A Sensor-Aided System for Physical Perfect Control Applications in the Continuous-Time Domain.

The recently introduced continuous-time perfect control algorithm has revealed a great potential in terms of the maximum-speed and maximum-accuracy behaviors. However, the discussed inverse model-originated control strategy is associated with considerable energy consumption, which has exceeded a technological limitation in a number of industrial cases. In order to prevent such an important drawback, several solutions could be considered. Therefore, an innovative perfect control scheme devoted to the multivariable real-life objects is investigated in this paper. Henceforth, the new IMC-related approach, strongly supported by the vital sensor-aided system, can successfully be employed in every real-time engineering task, where the precision of conducted processes plays an important role. Theoretical and practical examples strictly confirm the big implementation potential of the new established method over existing ones. It has been seen that the new perfect control algorithm outperforms the classical control law in the form of LQR (considered in two separate ways), which is clearly manifested by almost all simulation examples. For instance, in the case of the multi-tank system, the performance indices ISE, RT, and MOE for LQR without an integration action have been equal to 2.431, 2.4×102, and 3.655×10-6, respectively, whilst the respective values 1.638, 1.58×102, and 1.514×10-7 have been received for the proposed approach.

Alternative splicing is not a key source of chemerin isoforms diversity.

BACKGROUND: Chemerin is a chemoattractant protein with adipokine and antimicrobial properties encoded by the retinoic acid receptor responder 2 (RARRES2) gene. Chemerin bioactivity largely depends on carboxyl-terminal proteolytic processing that generates chemerin isoforms with different chemotactic, regulatory, and antimicrobial potentials. While these mechanisms are relatively well known, the role of alternative splicing in generating isoform diversity remains obscure. METHODS AND RESULTS: Using rapid amplification of cDNA ends (RACE) PCR, we determined RARRES2 transcript variants present in mouse and human tissues and identified novel transcript variant 4 of mouse Rarres2 encoding mChem153K. Moreover, analyses of real-time quantitative PCR (RT-qPCR) and publicly-available next-generation RNA sequencing (RNA-seq) datasets showed that different alternatively spliced variants of mouse Rarres2 are present in mouse tissues and their expression patterns were unaffected by inflammatory and infectious stimuli except brown adipose tissue. However, only one transcript variant of human RARRES2 was present in liver and adipose tissue. CONCLUSION: Our findings indicate a limited role for alternative splicing in generating chemerin isoform diversity under all tested conditions.

Stabilizing Differential Interfacial Curvatures by Mismatched Molecular Geometries: Toward Polymers with Percolating 1 nm Channels of Gyroid Minimal Surfaces.

Soft materials with self-assembled networks possess saddle-shaped interfaces with distributed negative Gaussian curvatures. The ability to stabilize such a geometry is critically important for various applications but can be challenging due to the possibly "deficient" packing of the building blocks. This nontrivial challenge has been manifested, for example, by the limited availability of cross-linkable bicontinuous cubic (Q) liquid crystals (LCs), which can be utilized to fabricate compelling polymers with networked nanochannels uniformly sized at ∼1 nm. Here, we devise a facile approach to stabilizing cross-linkable Q mesophases by leveraging the synergistic self-assembly from pairs of scalably synthesized polymerizable amphiphiles. Hybridization of the molecular geometries by mixing significantly increases the propensity of the local deviations in the interfacial curvature specifically required for Q assemblies. "Normal" (type 1) double gyroid LCs possessing 1 nm ionic channels conforming to minimal surfaces can be formulated by simultaneous hydration of the amphiphile mixtures, as opposed to the formation of hexagonal or lamellar mesophases exhibited by the single-amphiphile systems, respectively. Fixation of the bicontinuous network in polymers via radical polymerization has been efficaciously facilitated by the presence of the bifunctional polymerizable groups in one of the employed amphiphiles. High-fidelity lock-in of the ordered continuous 1 nm channels has been unambiguously confirmed by the observation of single-crystal-like diffraction patterns from synchrotron small-angle X-ray scattering and large-area periodicities by transmission electron microscopy. The produced polymeric materials exhibit the required mechanical integrity as well as chemical robustness in a variety of organic solvents that benefit their practical applications for selective transport of ions and molecules.

A Measurement-Aided Control System for Stabilization of the Real-Life Stewart Platform.

In the paper, an innovative control system devoted to the stabilization of the parallel manipulator-type Hexapod is presented. The device consists of three main parts, allowing us to reach the desired location during various external disturbances. Indeed, the telescopic boom located on the car along with the system providing the correction of the boom column deflection as well as the gyroscopic self-leveling head constitute a complex tool covering a plethora of modern techniques and solutions. Through the application of advanced issues strictly derived from nonlinear identification and multivariable control theory branches, the dynamical behavior of the discussed device has been handled in order to achieve a proper reference operation. Naturally, it has been supported by a set of accompanying approaches related to the processes of the real-time measurement and robust data transmission. It should be emphasized that the proposed computer-aided system is intended for the film industry, where image stabilization plays a crucial role. Such a statement has additionally been confirmed by other innovative products introduced by a company placed in Opole, Poland, called MovieBird International.

Improvement of Baro Sensors Matrix for Altitude Estimation.

The article presents the use of barometric sensors to precisely determine the altitude of a flying object. The sensors are arranged in a hexahedral spatial arrangement with appropriately spaced air inlets. Thanks to the solution used, the range of measurement uncertainty can be reduced, resulting in a lower probability of error during measurement by improving the accuracy of estimation. The paper also describes the use of pressure sensors in complex Tracking Vertical Velocity and Height systems, integrating different types of sensors to highlight the importance of this single parameter. The solution can find application in computational systems using different types of data in Kalman filters. The impact of pressure measurements in a geometric system with different spatial orientations of sensors is also presented. In order to compensate for local pressure differences, e.g., in the form of side wind gusts, an additional reference sensor was used, making the developed solution relevant for applications such as industrial ones.

Multipurpose monitoring system for edible insect breeding based on machine learning.

The Tenebrio molitor has become the first insect added to the catalogue of novel foods by the European Food Safety Authority due to its rich nutritional value and the low carbon footprint produced during its breeding. The large scale of Tenebrio molitor breeding makes automation of the process, which is supported by a monitoring system, essential. Present research involves the development of a 3-module system for monitoring Tenebrio molitor breeding. The instance segmentation module (ISM) detected individual growth stages (larvae, pupae, beetles) of Tenebrio molitor, and also identified anomalies: dead larvae and pests. The semantic segmentation module (SSM) extracted feed, chitin, and frass from the obtained image. The larvae phenotyping module (LPM) calculated features for both individual larvae (length, curvature, mass, division into segments, and their classification) and the whole population (length distribution). The modules were developed using machine learning models (Mask R-CNN, U-Net, LDA), and were validated on different samples of real data. Synthetic image generation using a collection of labelled objects was used, which significantly reduced the development time of the models and reduced the problems of dense scenes and the imbalance of the considered classes. The obtained results (average [Formula: see text] for ISM and average [Formula: see text] for SSM) confirm the great potential of the proposed system.

Solvent-assisted self-assembly of block copolymer thin films.

Solvent-assisted block copolymer self-assembly is a compelling method for processing and advancing practical applications of these materials due to the exceptional level of the control of BCP morphology and significant acceleration of ordering kinetics. Despite substantial experimental and theoretical efforts devoted to understanding of solvent-assisted BCP film ordering, the development of a universal BCP patterning protocol remains elusive; possibly due to a multitude of factors which dictate the self-assembly scenario. The aim of this review is to aggregate both seminal reports and the latest progress in solvent-assisted directed self-assembly and to provide the reader with theoretical background, including the outline of BCP ordering thermodynamics and kinetics phenomena. We also indicate significant BCP research areas and emerging high-tech applications where solvent-assisted processing might play a dominant role.

Pathway-Dependent Grain Coarsening of Block Copolymer Patterns under Controlled Solvent Evaporation.

Solvent evaporation annealing (SEA) is a straightforward, single-step casting and annealing method of block copolymers (BCP) processing yielding large-grained morphologies in a very short time. Here, we present a quantitative analysis of BCP grain-coarsening in thin films under controlled evaporation of the solvent. Our study is aimed at understanding time and BCP concentration influence on the rate of the lateral growth of BCP grains. By systematically investigating the coarsening kinetics at various BCP concentrations, we observed a steeply decreasing exponential dependence of the kinetics power-law time exponent on polymer concentration. We used this dependence to formulate a mathematical model of BCP ordering under nonstationary conditions and a 2D, time- and concentration-dependent coarsening rate diagram, which can be used as an aid in engineering the BCP processing pathway in SEA and also in other directed self-assembly methods that utilize BCP-solvent interactions such as solvent vapor annealing.