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).

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.

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.

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.

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.

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.

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.

Current Evidence Regarding Biomarkers Used to Aid Postoperative Delirium Diagnosis in the Field of Cardiac Surgery-Review.

Postoperative cognitive disorders after cardiac surgery may manifest as postoperative delirium (POD) or later as postoperative cognitive dysfunction (POCD). The incidence of POD after cardiac surgery ranges from 16% to 73%. In contrast to POD, POCD is usually diagnosed after the discharge from hospital, with an incidence of 30 to 70% of cases, very often noticed only by close relative or friends, decreasing after six (20-30%) and twelve (15-25%) months after surgery. Perioperative cognitive disorders are associated with adverse short- and long-term effects, including increased morbidity and mortality. Due to the complexity of delirium pathomechanisms and the difficulties in the diagnosis, researchers have not yet found a clear answer to the question of which patient will be at a higher risk of developing delirium. The risk for POD and POCD in older patients with numerous comorbidities like hypertension, diabetes, and previous ischemic stroke is relatively high, and the predisposing cognitive profile for both conditions is important. The aim of this narrative review was to identify and describe biomarkers used in the diagnosis of delirium after cardiac surgery by presenting a search through studies regarding this subject, which have been published during the last ten years. The authors discussed brain-derived biomarkers, inflammation-related biomarkers, neurotransmitter-based biomarkers, and others. Work based on inflammation-related biomarkers, which are characterized by the low cost of implementation and the effectiveness of delirium diagnosis, seems to be the closest to the goal of discovering an inexpensive and effective marker. Currently, the use of a panel of tests, and not a single biomarker, brings us closer to the discovery of a test, or rather a set of tests ideal for the diagnosis of delirium after cardiac surgery.

Development of a novel, high-affinity ssDNA trypsin inhibitor.

Inhibitors of serine proteases are not only extremely useful in the basic research but are also applied extensively in clinical settings. Using Systematic Evolution of Ligands by Exponential Enrichment (SELEX) approach we developed a family of novel, single-stranded DNA aptamers capable of specific trypsin inhibition. Our most potent candidate (T24) and its short version (T59) were thoroughly characterised in terms of efficacy. T24 and T59 efficiently inhibited bovine trypsin with Ki of 176 nM and 475 nM, respectively. Interestingly, in contrast to the majority of known trypsin inhibitors, the selected aptamers have superior specificity and did not interact with porcine trypsin or any human proteases tested. These included plasmin and thrombin characterised by trypsin-like substrate specificity. Our results demonstrate that SELEX may be successfully employed in the development of potent and specific DNA based protease inhibitors.

Polarization Gratings Spontaneously Formed from a Helical Twist-Bend Nematic Phase.

Spontaneous formation of polarization gratings by liquid crystalline phase made of bent dimeric molecules is reported. The grating is formed within the temperature range of the twist bend modulated nematic phase, NTB , without the necessity to pattern the cell surfaces, therefore the modulated nematic phase is a promising candidate for low-cost modulators and beam steering devices, the polarization properties of which depend on temperature. In addition, the study of the diffracted light properties turns out to be a sensitive measuring technique for determination of the 3D spatial variation of the optic axis in the cell.

Silencing of the nuclear RPS10 gene encoding mitochondrial ribosomal protein alters translation in arabidopsis mitochondria.

Hardly anything is known about translational control of plant mitochondrial gene expression. Here, we provide evidence for differential translation of mitochondrial transcripts in Arabidopsis thaliana. We found that silencing of the nuclear RPS10 gene encoding mitochondrial ribosomal protein S10 disturbs the ratio between the small and large subunits of mitoribosomes, with an excess of the latter. Moreover, a portion of the small subunits are incomplete, lacking at least the S10 protein. rps10 cells also have an increased mitochondrial DNA copy number per cell, causing an upregulation of all mitochondrial transcripts. Mitochondrial translation is also altered so that it largely overrides the hyperaccumulation of transcripts, and as a consequence, only ribosomal proteins are oversynthesized, whereas oxidative phosphorylation subunits are downregulated. Expression of nuclear-encoded components of mitoribosomes and oxidative phosphorylation system (OXPHOS) complexes seems to be less affected. The ultimate coordination of expression of the nuclear and mitochondrial genomes occurs at the complex assembly level. These findings indicate that mitoribosomes can regulate gene expression by varying the efficiency of translation of mRNAs for OXPHOS and ribosomal proteins.

Reordering transitions during annealing of block copolymer cylinder phases.

While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. Here, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene-block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the final horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.

The role of metalloproteinase ADAM17 in regulating ICOS ligand-mediated humoral immune responses.

Immune cells regulate cell surface receptor expression during their maturation, activation, and motility. Although many of these receptors are regulated largely at the level of expression, protease-mediated ectodomain shedding represents an alternative means of refashioning the surface of immune cells. Shedding is largely attributed to a family of a disintegrin and metalloprotease domain (ADAM) metalloproteases, including ADAM17. Although ADAM17 is well known to contribute to the innate immune response, mainly by releasing TNF-α, much less is known about whether/how this metalloprotease regulates adaptive immunity. To determine whether ADAM17 contributes to regulating adaptive immune responses, we took advantage of ADAM17 hypomorphic (ADAM17(ex/ex)) mice, in which ADAM17 expression is reduced by 90-95% compared with wild-type littermates. In this study, we show that that ADAM17 deficiency results in spleen and lymph node enlargement, as well as increased levels of Ag-specific class-switched Ig production following immunization with OVA together with anti-CD40 mAbs and polyinosinic-polycytidylic acid. Moreover, we demonstrate that the costimulatory ligand ICOS ligand (ICOSL) is selectively downregulated on the surface of B cells in an ADAM17-specific manner, although it is not proteolitically processed by recombinant ADAM17 in vitro. Finally, we show that higher cell surface levels of ICOSL in ADAM17(ex/ex) mice may contribute to the development of excessive Ab responses. Therefore, our data suggest a functional link between ADAM17 and ICOSL in controlling adaptive immune responses.

Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films.

Block copolymers spontaneously form well-defined nanoscale morphologies during thermal annealing. Yet, the structures one obtains can be influenced by nonequilibrium effects, including processing history or pathway-dependent assembly. Here, we explore various pathways for ordering of block copolymer thin films, using oven-annealing, as well as newly disclosed methods for rapid photothermal annealing and photothermal shearing. We report the discovery of an efficient pathway for ordering self-assembled films: ultrarapid shearing of as-cast films induces "latent alignment" in the disordered morphology. Subsequent thermal processing can then develop this directly into a uniaxially aligned morphology with low defect density. This deeper understanding of pathway-dependence may have broad implications in self-assembly.

Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy.

We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using in situ x-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, Δχ, that drives alignment and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding Δχ≈2×10^{-8}. From field-dependent scattering data, we estimate that grains of ≈1.2 µm are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

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.

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.

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.