Rational Principles Research Articles

Rapid Joule Heating Synthesis of Oxide-Socketed High-Entropy Alloy Nanoparticles as CO2 Conversion Catalysts.

The unorthodox surface chemistry of high-entropy alloy nanoparticles (HEA-NPs), with numerous interelemental synergies, helps catalyze a variety of essential chemical processes, such as the conversion of CO2 to CO, as a sustainable path to environmental remediation. However, the risk of agglomeration and phase separation in HEA-NPs during high-temperature operations are lasting issues that impede their practical viability. Herein, we present HEA-NP catalysts that are tightly sunk in an oxide overlayer for promoting the catalytic conversion of CO2 with exceptional stability and performance. We demonstrated the controlled formation of conformal oxide overlayers on carbon nanofiber surfaces via a simple sol-gel method, which facilitated a large uptake of metal precursor ions and helped to decrease the reaction temperature required for nanoparticle formation. During the rapid thermal shock synthesis process, the oxide overlayer would also impede nanoparticle growth, resulting in uniformly distributed small HEA-NPs (2.37 ± 0.78 nm). Moreover, these HEA-NPs were firmly socketed in the reducible oxide overlayer, enabling an ultrastable catalytic performance involving >50% CO2 conversion with >97% selectivity to CO for >300 h without extensive agglomeration. Altogether, we establish the rational design principles for the thermal shock synthesis of high-entropy alloy nanoparticles and offer a helpful mechanistic perspective on how the oxide overlayer impacts the nanoparticle synthesis behavior, providing a general platform for the designed synthesis of ultrastable and high-performance catalysts that could be utilized for various industrially and environmentally relevant chemical processes.

Fluorine‐Rich Covalent Organic Framework to Boost Electrochemical Kinetics and Storages of K+ Ions for Potassium‐Ion Battery

AbstractCovalent organic frameworks (COFs), featuring ordered nanopores with numerous accessible redox sites, have drawn much attention as promising electrode materials for rechargeable batteries. Thus far, however, COF‐based battery electrodes have exhibited limited capacity and unsatisfactory cycling stability due to the unwanted side reactions over their large surface area. Herein, a fluorine‐rich covalent organic framework (F‐COF) as an electrode material with improved stability and performance for potassium‐ion batteries is developed. The fluorinated COF not only stabilizes intercalation kinetics of K+ ions but also reinforces its electron affinity and conductivity, improving the reversibility of bond transitions during discharge–charge cycles. As a result, F‐COF affords a high specific capacity (95 mAh g−1 at fast rates up to 5 C) and excellent cycling stability (5000 cycles with ≈99.7% capacity retention), outperforming the pristine COF‐based electrodes devoid of F atoms. Notably, the experimental capacity of F‐COF approaches its theoretical value, confirming that a large proportion of electroactive sites are being actively utilized. Altogether, this work addresses the significant role of F atoms in improving the K+‐ion storage capability of COFs and provides the rational design principles for the continued development of stable and high‐performance organic electrode materials for energy storage devices.

High-Throughput Screening of Gas Sensor Materials for Decomposition Products of Eco-Friendly Insulation Medium by Machine Learning.

Nowadays, trifluoromethyl sulfonyl fluoride (CF3SO2F) has shown great potential to replace SF6 as an eco-friendly insulation medium in the power industry. In this work, an effective and low-cost design strategy toward ideal gas sensors for the decomposed gas products of CF3SO2F was proposed. The strategy achieved high-throughput screening from a large candidate space based on first-principle calculation and machine learning (ML). The candidate space is made up of different transition metal-embedded graphic carbon nitrides (TM/g-C3N4) owing to their high surface area and subtle electronic structure. Four main noteworthy decomposition gases of CF3SO2F, namely, CF4, SO2, SO2F2, and HF, as well as their initial stable structure on TM/g-C3N4 were determined. The best-performing ML model was established and implemented to predict the interaction strength between gas products and TM/g-C3N4, thus determining the promising gas-sensing materials for target gases with the requirements of interaction strength, recovery time, sensitivity, and selectivity. Further analysis guarantees their stability and reveals the origin of excellent properties as a gas sensor. The high-throughput strategy opens a new avenue of rational and low-cost design principles of desirable gas-sensing materials in an interdisciplinary view.

Hybrid Dynamic Covalent Network as a Protective Layer and Solid-State Electrolyte for Stable Lithium-Metal Batteries.

Lithium (Li) metal is a highly promising anode material for next-generation high-energy-density batteries, while Li dendrite growth and the unstable solid electrolyte interphase layer inhibit its commercialization. Herein, a chemically grafted hybrid dynamic network (CHDN) is rationally designed and synthesized by the 4,4'-thiobisbenzenamine cross-linked poly(poly(ethylene glycol) methyl ether methacrylate-r-glycidyl methacrylate) and (3-glycidyloxypropyl) trimethoxysilane-functionalized SiO2 nanoparticles, which is utilized as a protective layer and hybrid solid-state electrolyte (HSE) for stable Li-metal batteries. The presence of a dynamic exchangeable disulfide affords self-heability and recyclability, and the chemical attachment between SiO2 nanoparticles and the polymer matrix enables the homogeneous distribution of inorganic fillers and mechanical robustness. With integrated flexibility, fast segmental dynamics, and autonomous adaptability, the as-prepared CHDN-based protective layer enables superior electrochemical performance in half cells and full cells (capacity retention of 83.7% over 400 cycles for the CHDN@Li/LiFePO4 cell at 1 C). Furthermore, benefiting from intimate electrode/electrolyte interfacial contact, CHDN-based solid-state cells deliver excellent electrochemical performance (capacity retention of 89.5% over 500 cycles for the Li/HSE/LiFePO4 cell at 0.5 C). In addition, the Li/HSE/LiFePO4 pouch cell exhibits superior safety, even exposing various physical damage conditions. This work thereby provides a fresh insight into a rational design principle for dynamic network-based protective layers and solid-state electrolytes for battery applications.

Kierunki zmian strukturalnych i proceduralnych w administracji europejskiej

The subject of this article is the analysis of the basic directions of structural and procedural reforms in the European administration. Assuming, that only a well-worked out division of power may create a dynamic system, the author presents the actual conceptions of the task division between the central power and the local power. The structural changes at the central organs level are con- sidered by a prism of two problems: the adaptation of the institutional frames to the evolution in various fields of activity and the assurance of the effective coordination and control of this activity. In the field «of the territorial adminis- tration the changes are directed towards bringing the citizans closer to the centre of taking decisions, provided the principle of rationality is maintained. On the other hand, the reforms in the range of the administrative procedure lie in the „opening administration” for the citizans (gradual abolishing of traditional secrecy of the problems of general importance) new methods of management (implanting new planning, programming and budget systems).The author points out, that the complex „computarization” demands a count- erweight of the control laws, rules of systematization and preserving information about citizans. Finally, in the closing part of the article, the author presents the problem of codification of the administrative procedure, stressing that in the western countries the guiding idea of this procedure aims at the balance of two antagonistic forces: an individual and administration.

Quantifying Effects of Ligand-Metal Bond Covalency on Oxygen-Redox Electrochemistry in Layered Oxide Cathodes.

Oxygen-redox electrochemistry is attracting tremendous attention due to its enhanced energy density for layered oxide cathodes. However, quantified effects of ligand-metal bond covalency on the oxygen-redox behaviors are not fully understood, limiting a rational structure design for enhancing the oxygen redox reversibility. Here, using Li2Ru1-xMnxO3 (0 ≤ x ≤ 0.8) which includes both 3d- and 4d-based cations as model compounds, we provide a quantified relation between the ligand-metal bond covalency and oxygen-redox electrochemistry. Supported by theoretical calculations, we reveal a linear positive correlation between the transition metal (TM)-O bond covalency and the overlap area of TM nd and O 2p orbitals. Furthermore, based on the electrochemical tests on the Li2Ru1-xMnxO3 systems, we found that the enhanced TM-O bond covalency can increase the reversibility of oxygen-redox electrochemistry. Due to the strong Ru-O bond covalency, the thus designed Ru-doped Li-rich Li1.2Mn0.54Ni0.13Co0.13O2 cathode shows an enhanced initial coulombic efficiency, increased capacity retention, and suppressed voltage decay during cycling. This systematic study provides a rational structure design principle for the development of oxygen-redox-based layered oxide cathodes.

The role of single-boron of N-doped graphene for effective nitrogen reduction

Room-temperature electrocatalytic nitrogen reduction reaction (NRR) is of paramount significance for the fertilizer industry and fundamental catalysis science. However, many NRR catalysts were based on the use of metals. Herein, we focus on exploring boron-based, metal-free, efficient catalysts for NRR by density functional theory calculations with van der Waals corrections (DFT+D3). Our results show that the NRR performance of the boron active site can be improved by tuning the N-coordination environment in a graphene sheet, and the B-N-C structures show excellent stability. By considering the correlation between the Bader charges of the boron dopant over N-decorated graphene and their NRR activities, the rational design principle of a boron-based catalyst for NRR is developed. The boron-site with one pyridinic nitrogen in a double-vacancy structure is found to be a highly active center, with low reaction energy (0.53 eV) and kinetic barrier (0.84 eV) through the distal mechanism. We also found that the charge loss of boron considerably hampers hydrogen adsorption, which in turn promotes the NRR efficiency by hindering the competing hydrogen evolution. This work offers new insights into developing low-cost, highly effective boron-based materials as promising electrocatalysts for green ammonia synthesis.

Values of games over Boolean player sets

In this paper, we study new classes of value operators for coalitional games with players organized into a boolean algebra. Coalitional games are cooperative models in which players can form coalitions to maximize profit. The basic solution concepts in such game scenarios are value operators, which assign a unique real value to every player, reflecting thus selected principles of economic rationality. Some value concepts were extended beyond the classic coalitional model where every coalition of players can form. In particular, the extension of Shapley value exists for coalitional games in which players are partially ordered, and the feasible coalitions are the corresponding down-sets. Interestingly, this game-theoretic framework was employed in the method called Information Attribution. This method aims to solve the information decomposition problem, which asks for a particular additive decomposition of the mutual information between the input and target random variables. In such information-theoretic games, the players are predictors, and their set has the natural structure of a boolean algebra. Motivated by the original problem, we consider coalitional games where the players form a boolean algebra, and the coalitions are the corresponding down-sets. This more general approach enables us to study various value solution concepts in detail. Namely, we focus on the classes of values that can represent alternatives to the solution of the information decomposition problem, such as random-order values or sharing values. We extend the axiomatic characterization of some classes of values that were known only for the standard coalitional games.

Rational Chemical Design of Molecular Glue Degraders.

Targeted protein degradation with molecular glue degraders has arisen as a powerful therapeutic modality for eliminating classically undruggable disease-causing proteins through proteasome-mediated degradation. However, we currently lack rational chemical design principles for converting protein-targeting ligands into molecular glue degraders. To overcome this challenge, we sought to identify a transposable chemical handle that would convert protein-targeting ligands into molecular degraders of their corresponding targets. Using the CDK4/6 inhibitor ribociclib as a prototype, we identified a covalent handle that, when appended to the exit vector of ribociclib, induced the proteasome-mediated degradation of CDK4 in cancer cells. Further modification of our initial covalent scaffold led to an improved CDK4 degrader with the development of a but-2-ene-1,4-dione ("fumarate") handle that showed improved interactions with RNF126. Subsequent chemoproteomic profiling revealed interactions of the CDK4 degrader and the optimized fumarate handle with RNF126 as well as additional RING-family E3 ligases. We then transplanted this covalent handle onto a diverse set of protein-targeting ligands to induce the degradation of BRD4, BCR-ABL and c-ABL, PDE5, AR and AR-V7, BTK, LRRK2, HDAC1/3, and SMARCA2/4. Our study undercovers a design strategy for converting protein-targeting ligands into covalent molecular glue degraders.

Humanitarian expertise as a method of socio-humanitarian engineering (introduction to the ontology of humanitarian design)

The paper presents the conception of humanitarian expertise practice as a method. It is justified that the so-called post-non-classical situation allows coexistence of various ontologies and ontological patterns. It is presumed that these ontologies are project and human-created. The accustomed approaches of learning the world through objects and mastering the world in a necessary way are being replaced with an approach which measures, on the one hand, the constant transformation of the worlds, on the other – the metamorphoses and authors of the projects that go through their own process of changes together with humancreated worlds. The article presents the method of humanitarian expertise understood as the method of socio-humanistic engineering which implies construction and alteration of social worlds and management of metamorphosis of these changes. The author demonstrates that the transition to non-classical situation of self-determination is related to the replacement of the principle of human-sizedness of the world and the principles of objectivity, rationality and cognizability of the world with other patterns: that the world is not objective, not humanscaled, not sensible or rational. It is diverse – depending on the patterns of the designer. The article presents the principle scheme of this method. It describes the situation of launch and initiation of the project aimed not only at creation of new worlds but management of the metamorphosis of the changes in the authors of these changes. It is the unique feature of humanitarian projection and social engineering that differs from previously described experience and practice of the application of the project approach, where the authors of the projects were not the subject of reflexive self-projection.

Engineering interfaces to facilitate charge transport pathways in electrospun scaffolds for high-performance, flexible supercapacitors

Understanding and engineering the interface of a polymeric matrix with the ionic conductor offers important insights into the electrochemical charge polarization performance of flexible solid-state supercapacitors. These aspects are captured herewith utilizing chemically identical yet morphologically and interfacially different and distinct non-woven, electrospun polymeric membranes as scaffolds. Three distinct variations achieved through electrospinning namely, bilayered (PU/Ge) and core-shell geometries (PU@Ge and Ge@PU) with polyurethane (PU) and gelatin (Ge) are utilized in both conditions as polymeric electrolyte membranes for flexible supercapacitors. Equally important is the unique graphenic nanoplatelets (GNPs), fabricated through a single-step, template-driven approach, providing synergistic electrode/electrolyte interfaces. We unravel distinct changes in charge transport mechanism brought out by the interplay between surface chemistry and morphology of the electrospun scaffolds. The all-solid-state symmetric supercapacitor devices assembled with GNP@CC electrodes and PU/Ge, PU@Ge or Ge@PU polymeric membrane electrolyte of 1 M H3PO4 or EMIMBF4 are studied.Accordingly, the charge transport is protic and aprotic observed to switch from interfacial driven in the case of PU@Ge with H3PO4 to distinct phase separated ion transport channels in the case of PU/Ge with EMIMBF4. Thereby, a range of energy density (1.03–21.94 Wh kg−1), power density (0.049–99.97 kW kg−1) and scan rate operability (5–10,000 mV s−1) are demonstrated in such devices without any compromise on the cyclability. This study establishes rational design principles for tailoring the ion transport mechanism in a variety of matrices and thereby opens transformative possibilities for realizing high performance energy storage devices.

Modeling of the electromagnetic field based on rational mechanics approach

AbstractThis article discusses a possibility of deriving the basic equations of electrodynamics by means of the rational continuum mechanics principles and methods. We show that in order to give rise to the challenge, one needs to consider an elastic continuum of two‐spin particles of a special kind. We derive classical Maxwell's equations and discuss reasons limiting their application. After that, we propose more general equations that presumably provide a more correct description of the electromagnetic field.

Structural constraints link differences in neutralization potency of human anti-Eastern equine encephalitis virus monoclonal antibodies

Selection and development of monoclonal antibody (mAb) therapeutics against pathogenic viruses depends on certain functional characteristics. Neutralization potency, or the half-maximal inhibitory concentration (IC50) values, is an important characteristic of candidate therapeutic antibodies. Structural insights into the bases of neutralization potency differences between antiviral neutralizing mAbs are lacking. In this report, we present cryo-electron microscopy (EM) reconstructions of three anti-Eastern equine encephalitis virus (EEEV) neutralizing human mAbs targeting overlapping epitopes on the E2 protein, with greater than 20-fold differences in their respective IC50 values. From our structural and biophysical analyses, we identify several constraints that contribute to the observed differences in the neutralization potencies. Cryo-EM reconstructions of EEEV in complex with these Fab fragments reveal structural constraints that dictate intravirion or intervirion cross-linking of glycoprotein spikes by their IgG counterparts as a mechanism of neutralization. Additionally, we describe critical features for the recognition of EEEV by these mAbs including the epitope-paratope interaction surface, occupancy, and kinetic differences in on-rate for binding to the E2 protein. Each constraint contributes to the extent of EEEV inhibition for blockade of virus entry, fusion, and/or egress. These findings provide structural and biophysical insights into the differences in mechanism and neutralization potencies of these antibodies, which help inform rational design principles for candidate vaccines and therapeutic antibodies for all icosahedral viruses.

Perfektion in Technik und Form

Abstract Modern furniture manufacturing began in the mid-18th century, when cabinet makers, following the English model, manufactured luxury furniture in box construction and for stock according to the principles of rationalization and specialization. Other companies are used as examples to trace the transition to industrial production, until furniture made entirely by machines came onto the market at the beginning of the 20th century and the question of good design became increasingly important. Therefore, the second part of the essay uses selected examples to examine how companies were influenced from the outside, by large customers, the state or artists, with the aim of producing high-quality and well-designed products.

Adsorbate Bond Number Dependency for σ- and π-bonds in Linear Scaling Relationships

Despite the exigent role of heterogeneous catalysts, designing them in a bottom-up fashion remains a challenge. Linear scaling relationships are, thus far, perhaps the most auspicious first-principles design methodology relating adsorbate strength to catalyst activity. Yet, the successful application of scaling relations as a general design strategy, or even rationally breaking them, is still often limited to simple reactions such as σ-bond cleavage for monodentate adsorbates, and the relationships are nearly always established on close-packed surfaces. Here, it is discussed that for σ- and π-bonds, the metal–adsorbate system has opposite energetic dependency in the offset, which is directly related to the corresponding two classes of structure sensitivity that have empirically been observed in the literature for decades. The discussed observations imply that some currently invoked theories explaining the physical and chemical principles that dominate linear scaling relationships in both inter-adsorbate and BEP linear scaling relationships perhaps do not sufficiently explain them. The discussion is aimed at broadening the applicability of this rational design principle.

Specific features of student's self-identification in the comparative context of analysing socio-cultural characteristics of the society

Introduction. The article presents a comparative theorized review of the specific characteristics of students’ self-identification as main stakeholders of education, adapted to the conditions of mega-cultural challenges of social reality. Interest in the problem of student self-identity is determined by modern discussions about human identity, the specifics of its self-expression and existence in a rapidly and sometimes unpredictably changing social reality. The aim of the article is to identify the specific characteristics of the student's self-identification in the comparative context of analyzing socio-cultural characteristics of the society. Materials and Methods. The methodological basis of the study was sociocultural and systemic approaches. The authors used the principles of flexible rationality in building theorized constructs of the phenomenon of self-identity. The theory of ideal types (M. Veber) has the methodological value of the study, which makes it possible to navigate in the variety of manifestations of self-identification. The authors used the following research methods: a comparative historical method, deductive and chronological methods, generalization and analysis. Results. The authors have identified and analyzed specific features of students’ self-identification in the comparative context of the socio-cultural characteristics of modern society. It was revealed that students’ self-identification is influenced by a range of economic, geopolitical, digital and pandemic-related factors as well as communicative deviations, which can be subjective, objective, rational or irrational. In the course of this work the authors discovered that modern culture is perceived as a mosaic, rhizome, fragmentary-lipoid formation, in the semantic space of which the student is functioning (crisis of self-identification). The authors substantiate the idea that in philosophical discourse, the historical and cultural system of modern education contributes to the formation of an individual focused on observing rather than thinking. Thus, there is a strong need for rethinking the basic universals of professional education system, including self-identity construct (professional development, worldview, values, meanings, goals and aspirations). The authors highlight the essential problems of the phenomenon of self-identity as a complex self-evolving system and outline the patterns of organization of a student's meaningful life orientations in the space-time continuum of history and professional culture. Conclusions. The authors conclude about specific characteristics of students’ self-identification in the comparative context of analyzing socio-cultural characteristics of the society. The main content of student's self-identity is summarized with an emphasis on the harmony of interaction of the components of self-consciousness in certain cultural and historical situations, i.e. on the formation of the ability to solve professional problems with the correlation of one's own image of "I" with the fundamental moral values of the era, country and personal choice.

Biesta의 실천적 상호주관성 개념에 비추어 본 기술기반 미래학교 알트스쿨의 비판적 탐색

Objectives The purposes of this study were to critically investigate AltSchool, a technology-based future school that was once spotlighted for its innovative individualized model of learning, on the basis of Biesta’s concept of practical intersubjectivity. We hope to gain insights into what future education discourses should take into account by exploring the meaning of education.
 Methods We reviewed Biesta’s concept of practical intersubjectivity on the theoretical level and used it to analyze AltSchool’s curriculum and implementation. We particularly focused on the idea of understanding education as dynamic and reciprocal process of meaning making, which is thinking beyond subjectivism.
 Results AltSchool assumed education as individualized activities that follows rational and hierarchical principles and is acted out by individual sutdent subject and thus provided individualized learning that was guided by big data and algorithm. This approach overlooked the relational nature of education and caused teachers to take part mainly in technical interactions and accountability ambiguous. Moreover, it led to learnification of education in which spaces for cooperative inquiry on social and ethical responsibitilies of education were limited.
 Conclusions Critical reflection on the purpose of education in a holistic life and the meaning of education as practical intersubjectivity should serve as a focal point of the discourse on future education.

Implementation of Grant Management Policy and Social Assistance for the City of Bekasi

Grant spending must be managed in an orderly manner, in compliance with laws and regulations, efficiently, economically, effectively, transparently and responsibly with due observance of the principles of fairness, decency, rationality and benefits for society. The purpose of this study is to analyze the implementation of management, obstacles and solutions in the management of grants and social assistance based on the Minister of Home Affairs regulation number 32 of 2011. The method used is descriptive qualitative. The results show that the management of grant funds and social assistance at the Bekasi City Regional Financial and Asset Management Agency in 2018 has not been carried out properly. Some of the obstacles to managing grants and social assistance are the lack of staff, staff who have not received training regarding the management of grants, incomplete rules and procedures for managing grants, and overlapping allocations of funds in grant spending.

Description invariance: a rational principle for human agents

AbstractThis article refines a foundational tenet of rational choice theory known as the principle of description invariance. Attempts to apply this principle to human agents with imperfect knowledge have paid insufficient attention to two aspects: first, agents’ epistemic situations, i.e. whether and when they recognize alternative descriptions of an object to be equivalent; and second, the individuation of objects of description, i.e. whether and when objects count as the same or different. An important consequence is that many apparent ‘framing effects’ may not violate the principle of description invariance, and the subjects of these effects may not be irrational.

Algorithms for management of patients with severe A/H1N1 influenza: from diagnosis to respiratory support techniques. Guidelines

In 2022, the incidence of swine (A/H1N1) influenza markedly increased. It causes acute lung injury similar to that caused by SARS-CoV-2. These practice guidelines focus on the management of patients with severe influenza: from the diagnostic algorithm to the specifics of therapy and the use of respiratory support techniques. The guidelines provide recommendations on the rational pharmacotherapy principles: antiviral, antibacterial, mucoactive, anticoagulant, and symptomatic. The need to avoid prescribing drugs that may worsen the condition of patients with A/H1N1 influenza that are effective in other viral lung diseases, including SARS-CoV-2, has been pointed out. A detailed review of the criteria for initiation and principles of respiratory support is given.