General Synthesis Research Articles

Bimetal-bridging Nitrogen Coordination in Carbon-based Electrocatalysts for pH-universal Oxygen Reduction.

Electrocatalysts with atomically dispersed metal sites (e.g., metal-nitrogen-carbon) have been deemed as promising alternatives for noble-metal catalysts in couples of electrocatalytic reactions. However, the modulation of such atomic sites and the understanding of their interactions are still highly challenging. Herein, we propose a unique supermolecule assembly-profile coating strategy to prepare a series of diatomic electrocatalysts by profile coating of eight Prussian blue analogues (PBAs) on supramolecular supports respectively as bimetallic sources. The detailed microstructure analysis revealed that the metal-nitrogen-carbon sites with four- (Zn-N4 ) and five-coordination (Fe-N5 ) via the nitrogen coordination are similar to the cytochrome c oxidases. For promising electrocatalysis, such unique microstructure is able to activate oxygen molecules due to nitrogen-bonding coordination with bimetal sites, thus leading to efficient four-electron oxygen reduction in alkaline, neutral, and acid electrolytes. Especially, zinc group elements (e.g., Zn and Cd) with d10 electron configuration would significantly boost the nitrogen-bonding coordination with bimetal sites to enhance electrocatalytic activity. The proof-of-concept for the general synthesis of advanced electrocatalysts with controllable bimetal active sites and the mechanistic understanding will promote the promising electrocatalysis by applying the similar principles.

The Metabolic Regulation of Amino Acid Synthesis Counteracts Reactive Nitrogen Stress via Aspergillus nidulans Cross-Pathway Control.

Nitric oxide (NO) is a natural reactive nitrogen species (RNS) that alters proteins, DNA, and lipids and damages biological activities. Although microorganisms respond to and detoxify NO, the regulation of the cellular metabolic mechanisms that cause cells to tolerate RNS toxicity is not completely understood. We found that the proline and arginine auxotrophic proA5 and argB2 mutants of the fungus Aspergillus nidulans require more arginine and proline for normal growth under RNS stress that starves cells by accumulating fewer amino acids. Fungal transcriptomes indicated that RNS stress upregulates the expression of the biosynthetic genes required for global amino acids, including proline and arginine. A mutant of the gene disruptant, cpcA, which encodes the transcriptional regulation of the cross-pathway control of general amino acid synthesis, did not induce these genes, and cells accumulated fewer amino acids under RNS stress. These results indicated a novel function of CpcA in the cellular response to RNS stress, which is mediated through amino acid starvation and induces the transcription of genes for general amino acid synthesis. Since CpcA also controls organic acid biosynthesis, impaired intermediates of such biosynthesis might starve cells of amino acids. These findings revealed the importance of the mechanism regulating amino acid homeostasis for fungal responses to and survival under RNS stress.

Characterization of the Ligand Properties of Donor-stabilized Pnictogenyltrielanes.

A general synthesis and the characterization of novel alkyl-substituted NHC-stabilized pnictogenylboranes NHC ⋅ BH2 ER2 (NHC=N-heterocyclic carbene, E=P, As; R2 =Me2 , Ph2 , t BuH, Cy2 , (SiMe3 )2 ) are reported. These compounds were reacted with Ni(CO)4 to the corresponding complexes of the type [(NHC ⋅ BH2 ER2 )Ni(CO)3 ] to determine their donor strength by Tolman Electronic Parameters (TEPs) and their steric demand as ligands compared to classical phosphines, superbasic phosphines and other commonly applied donor systems. The results show that the NHC-stabilized pnictogenyltrielanes can be considered as being highly basic, while their steric influence depends strongly on the organic residues as well as the donor attached to the {BH2 } moiety. Although weaker than commonly used superbasic phosphines, the donor strength of pnictogenyltrielanes in general can be classified as of similar strength as NHCs. The steric and electronic properties can easily be modified by alkyl substitution as evident from the TEP trends.

Synthesis and Structural Elucidation of P-stereogenic Coumarins

This paper presents the general synthesis of a comprehensive group of P-chiral phosphinyl derivatives with a natural coumarin-type motif. A chiral substituent was attached at the third position of the coumarin molecule via the Knoevenagel procedure using readily available P-chiral phoshinylacetic acid esters without loss of enantiomeric purity. The application of salicylaldehyde-based derivatives allowed the incorporation of substituents of different electron character into the backbone of these coumarins making them suitable for subsequent chemical modifications. As a result, we gained access to six achiral (2a–g) and a large number ((Sp)-4a–f, (Sp)-6a–e and (Rp)-8a) of new potential chiral ligand precursors, pharmaceuticals, etc. with an imbedded phosphinyl group with evidenced biological activity based on the natural coumarin backbone. The molecular structure, including absolute configuration, was determined for seven compounds.

General Synthesis of High-Entropy Oxide Nanofibers.

The discovery of high-entropy oxides (HEOs) in 2015 has provided a family of potential solid catalysts, due to their tunable components, abundant defects or lattice distorts, excellent thermal stability (ΔG↓ = ΔH - TΔS↑), and so on. When facing the heterogeneous catalysis by HEOs, the micrometer bulky morphology and low surface areas (e.g., <10 m2 g-1) by traditional synthesis methods obstructed their way. In this work, an electrospinning method to fabricate HEO nanofibers with diameters of 50-100 nm was demonstrated. The key point lay in the formation of one-dimensional filamentous precursors, during which the uniform dispersion of five metal species with disordered configuration would help to crystallize into single-phase HEOs at lower temperatures: inverse spinel (Cr0.2Mn0.2Co0.2Ni0.2Fe0.2)3O4 (400 °C), perovskite La(Mn0.2Cu0.2Co0.2Ni0.2Fe0.2)O3 (500 °C), spinel Ni0.2Mg0.2Cu0.2Mn0.2Co0.2)Al2O4 (550 °C), and cubic Ni0.2Mg0.2Cu0.2Zn0.2Co0.2O (750 °C). As a proof-of-concept, (Ni3MoCoZn)Al12O24 nanofiber exhibited good activity (CH4 Conv. > 96%, CO2 Conv. > 99%, H2/CO ≈ 0.98), long-time stability (>100 h) for the dry reforming of methane (DRM) at 700 °C without coke deposition, better than control samples (Ni3MoCoZn)Al12O24-Coprecipitation-700 (CH4 Conv. < 3%, CO2 Conv. < 7%). The reaction mechanism of DRM was studied by in situ infrared spectroscopy, CO2-TPD, and CO2/CH4-TPSR. This electrospinning method provides a synthetic route for HEO nanofibers for target applications.

Novel N,S-Substituted naphthoquinone analogues from aminonaphthoquinones

In this study, novel N,S-substituted naphthaquinone analogues (2, 4, 6, and 8) were synthesized from the reactions of previously known aminonaphthaquinone derivatives (1, 3, 5, and 7) with allyl mercaptan. 2-(allylthio)-3-(4-phenylpiperazin-1-yl)naphthalene-1,4-dione (2), 2-(allylthio)-3-(4-(2-fluorophenyl)piperazin-1-yl)naphthalene-1,4-dione (4), 2-(allylthio) -3-(4-benzylpiperidin-1-yl)naphthalene-1,4-dione (6) and 2-(4-chlorophenylamino)-3-(allylthio)naphthalene-1,4-dione (8) were obtained from the reactions of 2-chloro-3-(4-phenylpiperazin-1-yl)naphthalene-1,4-dione (1), 2-chloro-3-(4-(2-fluorophenyl)piperazin-1-yl)naphthalene-1,4-dione (3), 2-(4-benzylpiperidin-1-yl)-3-chloronaphthalene-1,4-dione (5), and 2-(4-chlorophenylamino) -3-chloronaphthalene-1,4-dione (7) with allyl mercaptan according to the general synthesis procedure. Synthesized new naphthaquinone analogues (2, 4, 6, and 8) were purified by column chromatography. The chemical structures of these novel N,S-substituted naphthaquinone analogues were characterized by spectroscopic methods (FT-IR, NMR, and MS).

Continuidade espiritual das ideias de Abai e Blaise Pascal (Abai “Palavras de edificação”, B. Pascal “Pensamentos”)

Abstract: The purpose of the article is to identify the similarity of Abai’s and B. Pascal’s views regarding the categorical apparatus, key ideas, and specifics of the presentation. In the course of the study of this question, the historical-philosophical approach was chosen because of the need to study the core works in the context of the world’s history of thought. Hermeneutics was chosen to be the main method, which allows the free analysis and interpretation of texts, revealing their content from the perspective of non-classical forms of rationality. The eclectic method, together with general scientific analysis, synthesis, comparison and generalization in a complex, allows drawing parallels easily between directly unrelated sources and concepts. In the article, the belonging of Abai and B. Pascal’s philosophy to cordocentrism is determined, the categories of “heart”, “reason”, “will”, “faith”, “science” and their interconnection are revealed, the scope of genre affiliation of thinkers is expanded.

General and versatile synthesis of highly recyclable chiral phosphoric acid organocatalysts

We report a general and concise 9-step approach to heterogeneous chiral phosphoric acids and their application as highly recyclable organocatalysts in batch and continuous flow.

Cross-Domain Integration for General Sensor Data Synthesis: Leveraging LLMs and Domain-Specific Generative Models in Collaborative Environments

Cross-Domain Integration for General Sensor Data Synthesis: Leveraging LLMs and Domain-Specific Generative Models in Collaborative Environments

Sustainable Clothing Buying Behavior of Generations X and Y

This contribution addresses the sustainable clothing buying behaviour of Generations X and Y. The aim of the paper is to analyse the main features of sustainable clothing buying behaviour within Generations X and Y and to suggest some marketing activities for fashion companies. The theoretical background contains information from professional literature, scientific journals indexed in WOS and Scopus, and websites regarding the main trends in CSR, sustainable development, and sustainable buying behaviour, with a focus on the fashion industry. The analysis comprises multiple stages: the creation of a questionnaire through Google Forms, the selection of respondents from generations X and Y in the territory of the Slovak Republic, the analysis of respondents' answers through descriptive statistics, and the evaluation of research hypotheses via inductive statistics. Among the general research methods, historical-logical methods, analysis, synthesis, and comparison were used, whereas specialised research methods included methods of descriptive statistics and methods of inductive statistics implemented in the SPSS program. The questionnaire consisted of 11 questions based on previous research on the study topics and was completed by 139 respondents. The identification questions sought information from the participants about their identification as Generation X or Y, their gender, and their income. The next step was a comparison of shopping places, types of clothing, buying factors, and frequency and awareness of sustainable trends. The last 3 questions were framed according to previous research and were evaluated via descriptive statistics methods as well as inductive statistics. Research hypotheses are focused on relationships between the use of sustainable trends and belonging to a specific generation, the degree of influence of sustainable trends on buying behaviour and belonging to a specific generation, and the degree of rationality when purchasing clothes and belonging to a specific generation. On the basis of these tests, only the second hypothesis (influence of sustainable trends) was further analysed. Research results indicate that fashion brands can utilise slow fashion for different types of marketing communication to effectively target Generations X and Y, with a particular focus on influencer marketing on social networks. The limitations include various definitions of generations (birth years), possible cognitive distortions and the subjective answers of respondents. The fashion industry is an essential component of the creative industry and creative economy. Research could be extended by comparing sustainable clothing buying behaviour between inhabitants from the region with the above-average value of the regional NUTS3 creative index (Bratislava region) and inhabitants from other NUTS3 regions. Research could also be extended by comparing the effects of irrationality on generations in the context of behavioural economics. The end of the contribution expresses the benefits of this research for economics, the environment, and society.

Правовое обеспечение финансового суверенитета Российской Федерации в эпоху глобальных перемен

The article examines the issues of the formation of a modern legal model of financial relations aimed at strengthening the financial sovereignty of the state. Based on the analysis of financial legislation, law enforcement practice and legal doctrine, the author comes to the conclusion that it is necessary to carry out administrative reform aimed at integrating the Bank of Russia with the tasks of the Government of the Russian Federation to achieve the goals of sustainable economic development of the state. According to the author, the relations developing in the sphere of functioning of the financial system do not fit into the sectoral model of law. The use of general logical research methods, including analysis and synthesis, formal legal and comparative legal methods allowed the author to come to the following conclusions. 1. The formation of a modern model of financial and legal regulation, ensuring the strengthening of the financial sovereignty of the Russian Federation, should be based on administrative reform that creates conditions for the integration of the Bank of Russia with the tasks of the Government of the Russian Federation to achieve the goals of sustainable economic development of the state. 2. A balance between the tasks of the Government of the Russian Federation to achieve economic development goals and the goals of inflation targeting carried out by the Bank of Russia can be found through work to harmonize monetary and fiscal policy instruments - these two principles of managing the financial and credit mechanism. 3. In order to create a legal model of monetary circulation that prevents the withdrawal of capital and the legalization of proceeds from crime, it is necessary to carry out work to harmonize private law and public law methods of regulating financial relations. This will create the basis for the integration of legal instruments regulating the circulation of funds currently covered by different legal regimes.

Advanced Nano Research on Titanium Dioxide Nanoparticles: Prospects, General and Green Synthesis with Applications in Nanotechnology and Nanomedicine

Advanced Nano Research on Titanium Dioxide Nanoparticles: Prospects, General and Green Synthesis with Applications in Nanotechnology and Nanomedicine

О МЕСТЕ И РОЛИ ЛОКАЛИЗМОВ В СИСТЕМЕ НАЦИОНАЛЬНОГО ЯЗЫКА

The study of linguistic units operating as part of the national language within the framework of the regional usage is determined by the need to identify the features of heterogeneous variants and their place in the system of the national language, their relationship and interaction with the literary norm. The purpose of this article is to investigate the content of the linguistic term “localism” and distinguish it from other concepts used to denote territorially marked vocabulary. The article attempts to clarify the content of the linguistic term “localism” using examples from the Russian and Spanish languages, which occupies a central place in foreign linguistic regionalism. The theoretical basis of the study relies on the ideas of linguistic relativism and sociolinguistic determinism, according to which linguistic phenomena are studied taking into account variability as a fundamental property of language and in close relationship between language and social context. The methodological base is formed by general scientific methods, includingThe study of linguistic units operating as part of the national language within the framework of the regional usage is determined by the need to identify the features of heterogeneous variants and their place in the system of the national language, their relationship and interaction with the literary norm. The purpose of this article is to investigate the content of the linguistic term “localism” and distinguish it from other concepts used to denote territorially marked vocabulary. The article attempts to clarify the content of the linguistic term “localism” using examples from the Russian and Spanish languages, which occupies a central place in foreign linguistic regionalism. The theoretical basis of the study relies on the ideas of linguistic relativism and sociolinguistic determinism, according to which linguistic phenomena are studied taking into account variability as a fundamental property of language and in close relationship between language and social context. The methodological base is formed by general scientific methods, includingtheoretical analysis and synthesis of linguistic literature on the problem of regional vocabulary, as well as comparative analysis of terms denoting territorially marked language units. In the practical part of the study, the sociolinguistic interview method was used. General characteristics of localisms in Russian and Spanish are revealed. The conclusion about a stricter regulation of the use of localisms in the Spanish language is substantiated.

Bayes synthesis of multidimensional stochastic system with high availability by wavelet canonical expansions

Paper in devoted to methodological and instrumental software synthesis support for multidimensional stochastic systems with high availability (StSHA). For modeling of nonstationary stochastic processes (StP) it is supposed to implement wavelet canonical expansions (WLCE), based on coefficients of canonical expansions of covariance matrix using two dimensional orthonormal wavelet basis with compact carrier. Vector StSHA input and output are nonlinear on vector of random parameters with known probability density and Gaussian (normal) noise. Noises do not depend upon random parameters. Functional Bayes criterion (FBC) is presented by linear functional. Optimal system is synthesized using conditional risk criterion. General StSHA synthesis method and algorithm contains 4 steps and 7 positions. FBC optimal estimate is calculated by WLCE method. Special software is developed for scalar nonlinear StSHA. Results of computer experiments are given and discussed. His shown that high efficiency of method at 8 WLCE items. Directions of future investigations are presented.

Improvement of a municipal formation as an object of administrative and legal protection in the period from the formation of Russian statehood to the reforms of Peter the Great

The object of the study is such a concept as "landscaping", as well as its constituent elements at different stages of the development of the Russian state. In each of the periods of Russian history, the legislator determined in his own way what landscaping is, what measures to create a comfortable space for people's lives should be fixed in existing regulations, which bodies and organizations should be given powers of control and supervision in the sphere of public life in question, what specific powers (their nature and scope), as well as which sanctions for violations of the established requirements will be most commensurate with what has been done. In this regard, the interpretation of the concept of "landscaping", the selection of a definition that would be universal for all periods of the development of Russian statehood, is a controversial issue in modern science. Both general scientific and private scientific research methods were used in the preparation of the work. Thus, among the general scientific methods, analysis and synthesis were most widely used. Among the private scientific methods, the historical method is of key importance, since the subject of the study involves the study of different periods of the history of the Russian state, as well as the analysis of historical documents of the corresponding eras. In the course of the study, based on legislative acts of different eras, the constituent elements of the concept of "landscaping" inherent in a particular time are determined and a conclusion is formulated about the direct continuity of the development of this concept. As a result of the research, the author comes to the conclusion that in the early stages of the development of the Russian state, the era of Peter the Great is the most significant in the context of the development of landscaping as an object of administrative and legal protection. It was during this period that the elements of landscaping were isolated and legislatively fixed, as an activity that is provided by the state, administrative responsibility for many violations of the requirements for external landscaping of Russian cities was introduced for the first time, and the main vectors of further development in this area were laid and determined.

General Bandwidth Synthesis Approach for Multi-resolution SAR Imaging with Frequency Diverse Array

General Bandwidth Synthesis Approach for Multi-resolution SAR Imaging with Frequency Diverse Array

A General Synthesis Method for Patterning PEDOT toward Wearable Electronics and Bioelectronics.

The conductive polymer poly-3,4-ethylenedioxythiophene (PEDOT), recognized for its superior electrical conductivity and biocompatibility, has become an attractive material for developing wearable technologies and bioelectronics. Nevertheless, the complexities associated with PEDOT's patterning synthesis on diverse substrates persist despite recent technological progress. In this study, we introduce a novel deep eutectic solvent (DES)-induced vapor phase polymerization technique, facilitating nonrestrictive patterning polymerization of PEDOT across diverse substrates. By controlling the quantity of DES adsorbed per unit area on the substrates, PEDOT can be effectively patternized on cellulose, wood, plastic, glass, and even hydrogels. The resultant patterned PEDOT exhibits numerous benefits, such as an impressive electronic conductivity of 282 S·m-1, a high specific surface area of 5.29 m2·g-1, and an extensive electrochemical stability range from -1.4 to 2.4 V in a phosphate-buffered saline. To underscore the practicality and diverse applications of this DES-induced approach, we present multiple examples emphasizing its integration into self-supporting flexible electrodes, neuroelectrode interfaces, and precision circuit repair methodologies.

General synthesis of magnetic binary transition metal telluride nanocrystals

We demonstrate a general approach to synthesize ferromagnetic Cr2Te3 and FeTe2, paramagnetic CoTe2−x and NiTe2−x, and antiferromagnetic MnTe2 nanocrystals.

Supramolecular engineering cascade regulates NIR-II J-aggregates to improve photodynamic therapy.

Rational design of small organic molecule-based NIR-II photosensitizers (PSs) with high singlet oxygen quantum yield in aqueous solution for deep tissue imaging and cancer therapy still presents challenges. Herein, we devised a general synthesis strategy to obtain six NIR-II region PSs with tunable aggregation states by adjusting the steric effect, and all PSs possess longer NIR absorption/emission wavelengths with tails extending beyond 1200 nm. Notably, ATX-6 possessed a singlet oxygen quantum yield of 38.2% and exhibited concentration-dependent J-aggregation properties upon self-assembly in an aqueous solution. What's more, supramolecular engineering with DSPE-PEG2000 further enhanced its degree of J-aggregation, which was attributed to the dimer-excited reduction of the energy levels of the single-linear/triple-linear states and the facilitation of intersystem crossover processes. In addition, ATX-6 NPs showed superior photodynamic therapy effects and great potential in high-contrast in vivo bioimaging of the NIR-II region. These results provide valuable insights for achieving the diagnostic and therapeutic integration of tumors.

Intramolecular Coupling for General Synthesis of Backbone Substituted Bicyclo[1.1.1]pentyl Boronates

Intramolecular Coupling for General Synthesis of Backbone Substituted Bicyclo[1.1.1]pentyl Boronates