bluuebunny/crossref_metadata_2025 huggingface dataset:
Research on the Security Protection of Network Information Data by Blockchain Technology in the Context of Legal System
Authors: Jiang Fan
Published: October 2024

This paper examines the relevant legal system and integrates blockchain technology to ensure network information security protection at multiple levels, thereby meeting the requirements for network information security protection. The network information security protection effect of blockchain technology and initial technology is compared and analyzed. Subsequently, experiments such as SM2 encryption algorithm performance testing and analysis, anti-DDOS attack experiments, and anti-interception tests are conducted to prove the effectiveness and feasibility from the experimental point of view. The experiments reveal that the blockchain network information security protection test group always has a response time below 0.3s, resulting in higher protection efficiency. Compared to the RSA algorithm, the SM2 algorithm shows a shorter key length, which is more secure and efficient. The 2KB data encryption and decryption of the SM2 algorithm consume no more than 82.6 ms and 55 ms, respectively. With the increase in the attack rate, the transmission time of the DDOS attack detection mechanism fluctuates less, tends to be stable, and has excellent covertness, anti-attack, and transmission performance. This paper’s scheme satisfies the legal requirements, guaranteeing the highest level of data protection.
Pengaruh model pembelajaran kontekstual terhadap kemampuan membaca permulaan pada anak usia 5-6 tahun
Authors: Zannah Raudatul , Satriana Malpaleni , Rozie Fachrul
Published: October 2024

This research was motivated by the low initial reading skills of students in class B at Tiara Pertiwi Loa Janan Kindergarten, a problem was found, namely that more than half of the students in the class did not know the letters of the alphabet, factors that caused students' low initial reading skills, including inadequate learning models and media. effective. The aim of this research is to determine the influence of the contextual learning model on the beginning reading abilities of children aged 5-6 years at Tiara Pertiwi Loa Janan Kindergarten. This type of research is quantitative, namely using experimental research methods with the research type Quasi Experimental Design and the research design is Nonequivalent Control Group Design. The population in this study were all class B students at Tiara Pertiwi Loa Janan Kindergarten. The samples in this research were class B2 as the experimental class and class B4 as the control class. The initial reading ability data obtained were analyzed using descriptive statistics and inferential statistics in the SPSS 28.0 For Windows program. The results show that the posttest completeness percentage values ​​for the experimental class and control class are 100% and 20% respectively. The results of hypothesis testing using the Independent Sample T-test in the SPSS 28.0 For Windows program showed that Two-Sided p was 0.003, smaller than 0.05, thus H0 was rejected and H1 was accepted. The conclusion from the research results after treatment is that the contextual learning model has a significant effect on the beginning reading abilities of children aged 5-6 years at Tiara Pertiwi Loa Janan Kindergarten.  Using a contextual learning model with picture media and letter cards makes learning fun and more enthusiastic about recognizing letters.
Meningkatkan keterampilan motorik halus anak usia 5-6 tahun melalui kegiatan kolase dengan media bahan alam
Authors: Agysni Dhea Sasya , Alfarihah Atiqotul Maula
Published: October 2024

Motor skills are the ability to move parts of the body. Crawling, walking, running, and jumping are examples of motor skills. These skills are categorized into gross motor skills and fine motor skills. Good motor skills are not necessarily acquired by chance alone, but these skills must be acquired through sensory stimulation, teaching, and repeated practice. The focus of this research is only on the development of fine motor skills in children aged 5-6 years, where this skill is more difficult because it requires the ability to coordinate the body with small muscles, as well as training concentration and focus, self-control, and the need for more attention. Various activities can be carried out as an effort by parents and educators to develop fine motor skills, including collage activities. A collage is an activity of pasting and arranging materials systematically on the image surface. The materials used for collage activities in this research are natural in the form of seashells. This research uses quantitative research methods. The research object was Kober Harapan Kita Kalianda, South Lampung with a sample of 30 children aged 5-6 years. The independent variable in this research is collage activities using natural materials as media, while the dependent variable is the fine motor skills of children aged 5-6 years. The results of the t-test calculations in the experimental class are known to be sig, (2-tailed) of 0.00. This sig (2-tailed) value is smaller than 0.05 (5%) which means that Ha is accepted and Ho is rejected. So it can be concluded that collage activities using natural materials as media affect the fine motor skills of children aged 5-6 years in Kober Harapan Kita Kalianda, South Lampung Regency.
Peningkatan kemampuan mengenal huruf melalui media kartu kata bergambar pada anak kelompok B2 di TK IT Salsabila Samarinda
Authors: Sari Padia Nadila , Razak Abdul , Nurwati Nurwati
Published: October 2024

This research was motivated by the wlow wability wto wrecognize wchildren's wletters wby wlooking wat wthe wresults wof wpre-action wobservations won wJuly w20 w2022 wwhich wshowed wthat wthe wability wto wrecognize wletters wof wchildren win wthe wB2 wgroup wat wTK wIT wSalsabila wSamarinda wwas w12%. wChildren's wability wto wrecognize wletters whas wnot wyet wdeveloped woptimally, wbecause wthere ware wsome wstudents wwho ware wstill wunable wto wrecognize wletters, wcannot wdistinguish wletters, wand wstill whave wdifficulty win wputting wwords wtogether winto wsimple wsentences. wBecause wmany wchildren wthere wstill wdon't wunderstand wthe wconcept wof wwords, wso wthey whave wdifficulty wnaming wletters wwith wsimilar wpronunciations wand wshapes. wThis wresearch waims wto wdetermine wthe wincrease win wthe wability wto wrecognize wletters wthrough wthe wmedia wof wpicture wword wcards win wgroup wB2 wchildren wat wthe wSalsabila wIT wKindergarten, wSamarinda. wThis wresearch wis wClassroom wAction wResearch w(PTK). wThe wsubjects wof wthis wresearch wwere w12 wchildren waged w5-6 wyears wat wthe wSalsabila wIT wKindergarten win wSamarinda, wconsisting wof w4 wchildren wof weither wgender w(boys) wand w8 wchildren wof wthe wsame wgender w(girls). wData wCollection wTechniques wwith wObservation wand wDocumentation. wThis wresearch wwas wcarried wout win wII wcycles, wthe wstages win wthis wresearch wfollowed wClassroom wAction wResearch w(PTK) wprocedures wincluding: w(1) wPlanning, w(2) wImplementation, w(3) wObservation wor wobservations, w(4) wReflection. wBased won wthe wresults wof wthis wresearch, wit wshows wthat wusing wpicture wword wcard wmedia wcan wimprove wchildren's wability wto wrecognize wletters. wThis whas wbeen wproven win wthe wimplementation wof wcycle wI wwhere wit wreached w35% wand win wcycle wII wit wincreased waccording wto wthe wresearcher's wtarget wof wreaching w81%. wThe wresults wof wresearch won wincreasing wthe wability wto wrecognize wletters wthrough wpicture wword wcards win wgroup wB2 wchildren wat wthe wSalsabila wIT wKindergarten win wSamarinda ware wsaid wto whave wincreased waccording wto wthe wresearchers' wexpectations. wUsing wpicture wword wcard wmedia wmeans wchildren wdon't wget wbored wquickly wand wlearning wwill wbe wfun wand wthey wwill wbe wmore wenthusiastic wabout wlearning wto wrecognize wletters.
Bermain yang bermakna: apakah konsep merdeka bermain pada fase pondasi sudah merdeka?
Authors: Paula Zihan Fauziah Noor , Agustin Mubiar
Published: October 2024

Abstrak
Konsep bermain bermakna yang terdapat pada kurikulum merdeka untuk fase pondasi menjadi konsep yang berupaya mewujudkan bermain yang bermakna bagi anak. Dalam implementasinya tercatat 42,8% satuan PAUD di Indonesia telah menerapkan merdeka bermain. Akan tetapi konsep merdeka bermain nyatanya belum sepenuhnya dimaknai dalam implementasinya. Penelitian ini berupaya mengkaji lebih dalam terkait implementasi makna ‘merdeka’ pada konsep merdeka bermain dalam pembelajaran di satuan pendidikan. Pada penelitian ini, konsep merdeka bermain ditelaah menggunakan teori bermain kontemporer. Metode yang digunakan pada penelitian ini yaitu kualitatif eksploratif dengan teknik pengambilan data observasi partisipatif yang dilakukan peneliti pada kegiatan workshop implementasi kurikulum merdeka Kab. Bandung, teknik wawancara tidak terstruktur pada 8 guru PAUD, dan teknik liblary research. Dari penelitian yang telah dilaksanakan peneliti berargumen bahwa makna ‘merdeka’ dalam merdeka bermain belum sepenuhnya terwujud dikarenakan berbagai masalah dilapangan yang berimbas pada kurang optimalnya implementasi konsep merdeka bermain. Padahal seharusnya merdeka bermain bisa memberikan pengalaman bermain bermakna bagi anak yang bertujuan untuk memberikan suasana belajar yang menyenangkan serta meningkatkan kualitas pembelajaran, yang akan berdampak pada proses stimulasi perkembangan anak.
Kata Kunci: Merdeka Bermain, Bermain Bermakna, Kurikulum Merdeka
Identity confusion and depression in groups of adolescents having psychiatric and physical symptoms
Authors: Çuhadaroğlu Füsun
Published: October 2024

The aim of this study was to investigate the identity status of adolescents having psychiatric and physical symptoms and the relation of depression with identity problems in adolescence. Three groups of university students were given a sociodemographic questionnaire, Beck Depression Inventory (BDI) and Sense of Identity Assessment Form (SIAF). The first group consisted of 31 students who were seen by the consultant psychiatrist at the Student Health Center of a university in Ankara. The second group included 37 students who applied to the same center with various physical complaints but did not need to be consulted by the psychiatrist. The third group was a group of 50 healthy students at the same university. The analysis revealed that only those with psychiatric complaints had identity confusion and that for the males in this group depressive symptoms are significant predictors of identity confusion.
Women and Social Security in Iraq
Authors: د. شيلان علي عارف
Published: October 2024

Abstract
The concept of social security has turned into a dream that everyone seeks in most parts of the world, such as the countries of the Middle East, especially Iraq. Due to successive wars and the collapse of political systems one after another, this led to instability, and the concept of social security became a question that everyone tries to answer and search for ways to reach. Therefore, in this research, I studied the concept of social security, its origins and development in the West, as well as the emergence of the concept and how to address it in Islamic countries, and focused on the concept of social security in Iraq. The concept of social security and its related notions to the status of women in Middle Eastern countries were also studied. The comparative analytical method was used to study this concept. The results revealed that the concept of social security has developed significantly to include numerous dimensions and is applied in various fields. The concept has also developed from simply searching for security and safety to laws that are applied in social security.
Comparative study of double and dual electroinduction spherical electric field strength sensors
Authors:   Omsk State Technical University, Biryukov S. V.
Published: October 2024

The work provides a comparative study of double and dual electric field strength sensors. The comparison examined the design, technological and metrological parameters of the sensors, as well as the complexity of their measuring circuits. Research has revealed similarities in the design and technological parameters of the sensors and differences in metrological characteristics and the complexity of the measuring circuits. In terms of metrological characteristics, dual sensors are significantly superior to double ones. It has been established that a dual sensor having sensitive elements with angular dimensions 1=46,38 , and 2=90 , has a smaller error due to field inhomogeneity. The error does not exceed  ±2,76 % in the spatial measurement range 0a1. With the same error, double sensors can only be used in a limited spatial measurement range of 0a0,89. It is shown that dual sensors are superior to dual sensors in terms of metrological parameters. This indicates the advisability of their use.
Efecto de las plantaciones forestales no nativas de pinos y eucaliptos en los vertebrados terrestres: Una revisión descriptiva sobre los trabajos realizados en la Argentina
Authors: Schaaf Alejandro A. , Nadalino Rioja Juan M- , Reppucci Juan I. , Ruggera Román A.
Published: October 2024

En las últimas décadas, las plantaciones monoespecíficas con árboles no nativos crecieron en diferentes regiones del mundo. En la Argentina se está fomentando este tipo de producción, causando un reemplazo del paisaje nativo y pudiendo afectar a distintos grupos de animales. Por tal motivo, en este trabajo realizamos una revisión bibliográfica acerca de lo que se sabe y los vacíos de información sobre los efectos de las plantaciones no nativas de pinos y eucaliptos en los vertebrados terrestres en diferentes ecorregiones del país. Encontramos un total de 34 artículos publicados, de los cuales 48% se enfocó en el impacto de las plantaciones de pinos y eucaliptos sobre vertebrados. Los grupos taxonómicos más estudiados fueron las aves y los mamíferos terrestres medianos y grandes, sobre todo en las ecorregiones Selva Atlántica y Bosques Patagónicos. Los efectos más reportados fueron la disminución de la riqueza, los cambios en la composición de especies y el menor uso de las plantaciones no nativas por parte de los distintos grupos de vertebrados. El tipo de manejo de las plantaciones, sobre todo en cuanto a la conservación del sotobosque y la conectividad con el bosque nativo, sería clave para disminuir el impacto negativo sobre las especies de vertebrados. Además, encontramos que todavía existen vacíos de información en ciertas ecorregiones y grupos de vertebrados (e.g., herpetofauna y mamíferos pequeños). Por lo tanto, sugerimos que se incentive esta clase de estudios en diferentes regiones del país para dar a conocer los efectos de este tipo de actividad antrópica, y también para garantizar la buena gestión y conservación de los ambientes nativos aledaños y el flujo genético de las poblaciones de la biodiversidad asociada.
Using Eye Tracking to Expose Cognitive Processes in Understanding Conceptual Models
Authors: Bera Palash , Soffer Pnina , Parsons Jeffrey
Published: October 2024

Conceptual models are used to communicate information about a domain during the development of information systems. In two experimental studies using business process models, we demonstrate how eye tracking can contribute to understanding the cognitive processes by which readers use conceptual modeling scripts to perform problem solving tasks. In the first study, we compare scripts generated using two process modeling grammars and demonstrate how attention paid to specific parts of scripts generated using grammar variations, and differences in visual association between parts of a diagram, account for task performance. In the second study, we use a combination of eye tracking and verbal protocol analysis to examine how visual association between parts of conceptual modeling scripts can indicate cognitive integration while performing problem solving tasks. The studies show that task performance can be explained with different mental processes, reflected in specific eye tracking behavior, where scripts developed following different rules invoke different cognitive processes. We show that attention can be measured by eye tracking and can explain task performance. In addition, we show that visual association (which is observable) between parts of a modeling script involves cognitive integration (which is not observable). This finding can be used to improve conceptual modeling grammars in several ways, including understanding the effects of alternative visual arrangements of models on how effectively they communicate domain knowledge for particular tasks, and guiding the design of visual modeling notations.
Fake News on Social Media: People Believe What They Want to Believe When it Makes No Sense At All
Authors: Moravec Patricia L. , Minas Randall K. , Dennis Alan R.
Published: October 2024

Fake news (i.e., misinformation) on social media has sharply increased in the past few years. We conducted a behavioral experiment with EEG data from 83 social media users to understand whether they could detect fake news on social media, and whether the presence of a fake news flag affected their cognition and judgment. We found that the presence of a fake news flag triggered increased cognitive activity and users spent more time considering the headline. However, the flag had no effect on judgments about truth; flagging headlines as false did not influence users’ beliefs. A post hoc analysis shows that confirmation bias is pervasive, with users more likely to believe news headlines that align with their political opinions. Headlines that challenge their opinions receive little cognitive attention (i.e., they are ignored) and users are less likely to believe them.
Peer Effects in Competitive Environments: Field Experiments on Information Provision and Interventions
Authors: Li Zhuoxin , Wang Gang , Wang Harry Jiannan
Published: October 2024

Prior studies of social-norms interventions have focused on nudging behavior in noncompetitive settings. This research evaluates such interventions in competitive environments, for example, a class with a competitive grading policy. Field experiments on a learning management system show that providing descriptive information about peers’ behavior has mixed effects in reducing procrastination and improving performance outcomes. Specifically, the effects are moderated by individual characteristics and contextual variables. First, peer information interventions are more effective for males, and the effects are stronger in a male-majority environment than in a female-majority environment. These findings differ from prior studies of social-norms interventions conducted in noncompetitive settings, in which females are found to be more responsive to interventions. Gender differences in our competitive settings can be explained by males’ and females’ differential preferences for competition: males are more competitive-oriented and thus are more responsive to peer information in competitive environments. Second, we find that individuals who are in great need of interventions, that is, those with poor past behavior and performance, are also more likely to benefit from peer information interventions, suggesting that peer information interventions motivate positive change. This study highlights the heterogeneous effects of peer information interventions and has implications for targeted interventions.
МОТИВ УЯЗВИМОГО МЕСТА В ОСЕТИНСКОМ ЭПИЧЕСКОМ ФОЛЬКЛОРЕ
Authors:   V. I. Abaev North Ossetian Institute for Humanitarian and Social Studies, DARCHIEVA Madina
Published: October 2024

A motif as one of the most important elements of a plot is always interesting to folklore researchers. The Ossetian epic folklore consists of Narts Sagas, Legends of Tsartsyata and Legends of Daredzanta. The purpose of this study is to analyze the vulnerability motif in Ossetian folklore. The relevance of the study is substantiated by the understudied nature of the motif of the vulnerable place on the invulnerable body of the epic, which is frequent in the Ossetian epic. The novelty of the research lies in the complex consideration of epic folklore, including three known cycles, as well as in the discovery of not only major but also minor plots containing the mentioned motif. The following tasks are being solved in order to achieve this goal: identification of plots containing the motif in question; classification of varieties of vulnerability in Ossetian folklore; attraction of data from some Caucasian national versions of the Narts epic for a more structured analysis; gradation of universal and specific features of the motif's functioning. The study revealed various types of epic hero's vulnerability, noted their connection to the plot in accordance with the performing tradition and variation of the folklore text; revealed the connection of the motif of a vulnerable place on the body of an invulnerable hero with the somatic code of culture. The most vivid examples here are the images of Soslan and Batraz, and the above motif is connected with the plots of birth, hardening and death of heroes. Vulnerability from their own weapons is characteristic of both the Narts and their enemies. At the same time, in Ossetian Narts Sagas there are heroes whose soul is thought to be outside the body, which corresponds to ancient animalistic ideas. This type of vulnerability reveals an Indo-European tripartite nature. The invulnerability achieved by the heroes through miraculous military equipment and armour is conventional and is associated with the armour / chain mail of Tserek (Tserechy zğær) and the helmet of Bidas (Bidasy taka). In the Ossetian epic, in addition to the vulnerability of the physical body, there is a vulnerability of a psychosomatic nature, peculiar to a certain kind of heroes and found in the story of the marriage of Nart Khamyts. Cross-genre analysis of the vulnerability motif in Ossetian folklore as a whole, as well as its comparative study in all Caucasian versions of the Narts epic is promising.
АРХАИЧЕСКИЕ ПЛАСТЫ И ИСЛАМСКИЕ ВОЗЗРЕНИЯ В ТАТАРСКОЙ ВЕРСИИ ДАСТАНА «ТУЛЯК»
Authors:   G. Ibrahimov Institute of Language, Literature and Art, MUKHAMETZYANOVA Liliya
Published: October 2024

The Tatar version of the archaic-heroic dastan about Tulyak and Susylu deeply reflects the worldviews of the Turkic peoples, while preserving the poetic significance of Tatar folk art in a peculiar way; contains laconism, heroism, adventure character; handwritten copies of Tulyak convey historical memory, the continuity of generations to the present day. The unexplored Tatar version of dastan as a source of the epic culture of the ethnic group determines the relevance of the stated topic. The article systematizes all known variants of the national version of this folklore piece. The purpose of the article is to determine the originality of the Tatar version of the Tulyak dastan as a whole. As part of the description of the variants, the author gives a detailed description of the texts of the Tatar variants of the dastan, determines that to date only six variants of the Tatar Tulyak have been found; notes the lexical, stylistic, semantic differences between the variants, the time and place of rewriting, etc. features of the texts. He emphasizes that each variant of the Tulyak dastan is equally valuable and has great scientific significance. In addition, the author's scientific interest includes clarifying the role of mythological and religious views of the ethnic group in the book version of the Tulyak dastan; revealing the specifics of Tatar variants of the dastan against the background of versions of other Turkic peoples, in particular, the Bashkir version. The article also notes the vitality of the plot not only in the form of a book version of the epic, but also in the oral work of the Tatars; using the example of the most complete texts, some mythological representations of the Tatars in this work are investigated; attention is drawn to the fact that in the texts, along with Muslim beliefs, traces of archaic elements of the traditional worldview of the ancient Turks are well preserved. The scholarly novelty of the study consists in a comprehensive analysis of all known Tatar variants of the Tulyak dastan, focusing on the reflection of the ethnic worldview in the epic. The source of the study was the Tatar-language texts of the Tulyak dastan, found in different years in places of compact residence of the ethnic group. In the study, the author applied structural-descriptive, textual, and germanicistic research methods. As a result, it is proved that the Tatar Tulyak dastan, expressing and transmitting the spiritual experience and creative consciousness of the people, has its rightful place in the continuous process of epic development. The potential of the topic for further study of the problem is very high.
Linker Engineering in Fluorinated CeIV-based Metal-Organic Frameworks: Impact on Cooperative CO2 Adsorption and Biogas Upgrading Potential
Authors: Nerli Francesca , Guiotto Virginia , Nardelli Francesca , Giovanelli Andrea , Bizzarro Linda , Zizzi Federico , Geppi Marco , Calucci Lucia , Crocellà Valentina , Lessi Marco , Taddei Marco
Published: October 2024

Understanding fundamental aspects related to the adsorption behaviour of flexible metal-organic frameworks (MOFs) is a crucial step to develop improved sorbents for gas separations. F4_MIL-140A(Ce) is a recently discovered MOF that displays a cooperative CO2 adsorption mechanism enabled by concerted rotation of the aromatic rings of the tetrafluoroterephthalate linkers, giving rise to a step-shaped isotherm. Here, we shed light on the key role played by the degree of fluorination of the organic linker in such a cooperative mechanism by synthesising novel Fx_MIL-140A(Ce) (where x = 2 or 3) analogues and characterising them with a wide range of experimental techniques, including powder X-ray diffraction, thermogravimetric analysis, solid state nuclear magnetic resonance spectroscopy, gas sorption analysis, in situ infrared spectroscopy and adsorption microcalorimetry. We found that the removal of fluorine atoms from the linker switches off the cooperative mechanism observed in the perfluorinated prototype, leading to Langmuir-type CO2 adsorption isotherms for Fx_MIL-140A(Ce). This is accompanied to a higher CH4 adsorption capacity, which results in a progressive decrease in CO2/CH4 selectivity. Desorption of the crystallisation water coordinated to CeIV from Fx_MIL-140A(Ce) appears to induce a similar phase transition to that observed in F4_MIL-140A(Ce), suggesting that a cooperative mechanism persists when water is the adsorbate. The accessibility of CeIV sites in evacuated Fx_MIL-140A(Ce) is confirmed, although their Lewis acidity decreases at lower degrees of fluorination, due to the reduced electron-withdrawing character of the aromatic ring.
Triacylphosphines as a Novel Class of Phosphorus Sources for the Synthesis of Transition Metal Phosphide Nanoparticles
Authors: Antanovich Artsiom , Iodchik Andrey , Li Jing , Khavlyuk Pavel , Shamraienko Volodymyr , Lesnyak Vladimir
Published: October 2024

Transition metal phosphide (TMP) nanoparticles (NPs) have emerged as a versatile material for a wide array of energy conversion/storage applications due to their robustness and a broad range of available compositions, stoichiometries, and crystalline structures. Combined with size and shape control, this opens many possibilities to tailor NPs’ electronic, physical, and chemical properties. One of the main hurdles towards broader implementation of TMP NPs consists in their challenging synthesis further exacerbated by the limited choice of available phosphorus precursors. On the one hand, the synthesis of TMP NPs can be carried out using various alkyl- or arylphosphines, which require prolonged heating at high temperatures, while on the other hand, the use of highly reactive P(SiMe3)3, white phosphorus, or PH3 poses additional obstacles associated with their hazardous nature, high cost, and limited availability. In this work, we report the use of acylphosphines as a new class of phosphorus sources for the synthesis of nickel and cobalt phosphide NPs. We demonstrate that they react with respective metal chlorides at moderate temperatures as low as 250 °C yielding amorphous/poorly crystalline NPs, which can later be crystallized at 305 °C. After ligand stripping with HPF6, the prepared NPs were shown to be an effective electrocatalyst for the hydrogen evolution reaction in the acidic medium exhibiting overpotentials as low as 50 mV at a current density of 10 mA/cm², which is among the lowest overpotentials for these materials and is quite competitive to commercial platinum-based catalysts.
Divergent Activity Shifts of Sn-Based Catalysts for Electrochemical CO2 Reduction: pH-Dependent Behavior of Single-Atom vs. Polyatomic Structures
Authors: WANG Yuhang , Zhang Di , Sun Bin , Jia Xue , Zhang Linda , Cheng Hefeng , Fan Jun , Li Hao
Published: October 2024

Tin (Sn)-based catalysts have been widely studied for electrochemical CO2 reduction reaction (CO2RR) to produce formic acid, but the intricate influence of the structural sensitivity in single-atom Sn (e.g., Sn-N-C) and polyatomic Sn (e.g., SnOx and SnSx; x=1,2) on their pH-dependent performance remains enigmatic. Herein, we integrate large-scale data mining (with >2,300 CO2RR catalysts from available experimental literature during the past decade), ab initio computations, machine learning force field accelerated molecular dynamic simulations, and pH-field coupled microkinetic modelling to unravel their pH dependence. We reveal a fascinating contrast: the electric field response of the binding strength of *OCHO on Sn-N4-C and polyatomic Sn exhibits opposite behaviors due to their differing dipole moment changes upon *OCHO formation. Such response leads to an intriguing opposite pH-dependent volcano evolution for Sn-N4-C and polyatomic Sn. Subsequent experimental validations of turnover frequency and current density under both neutral and alkaline conditions well aligned with our theoretical predictions. Most importantly, our analysis suggests the necessity of distinct optimization strategies for *OCHO binding energy on different types of Sn-based catalysts.
Hydroalkylation of Vinylarenes via Transition Metal-Free In-Situ Generation of Benzylic Nucleophiles using Tetramethyldisiloxane and KOtBu
Authors: St-Onge Piers , Nugraha Hana , Newman Stephen
Published: October 2024

Hydrosilanes and Lewis bases are known to promote various reductive defunctionalizations, rearrangements, and silylation reactions, facilitated by enigmatic silicon/Lewis base-derived reactive intermediates. Despite the wide variety of transformations enabled by this reagent combination, no examples of intermolecular C(sp3)–C(sp3) forming reactions have been reported. In this work, we’ve identified 1,1,3,3-tetramethyldisiloxane (TMDSO) and KOtBu as a unique reagent combination capable of generating benzylic nucleophiles in-situ from styrene derivatives, which can subsequently react with alkyl halides to give a new C(sp3)–C(sp3) linkage via formal hydroalkylation. Mechanistic experiments suggest that the reaction proceeds through a key hydrogen atom transfer (HAT) step from a hydrosilane reducing agent to styrene, affording a benzylic radical that undergoes reductive radical polar crossover (RRPC) and subsequent SN2 alkylation.
Quantification of arginine rich cyclic cell-penetrating peptide-lipid-conjugates using trifluoracetic acid-based UPLC-MS/MS analysis
Authors: Bay Cindy , Uhl Philipp , Burhenne Jürgen , Haefeli Walter E. , Sauter Max
Published: October 2024

Lipid-based drug delivery systems can be surface modified by lipid-conjugates of the pertinent substance. Prominent modifica-tions include arginine-rich cell-penetrating peptides (CPP). Toxicokinetic evaluation of these lipid-conjugates is important during pre- and clinical development of drug-delivery formulations. Due to their amphiphilic character and high number of basic amino acid residues, lipid-conjugates of CPP exhibit challenging characteristics in regard to their plasma bioanalysis with LC-MS/MS instruments. These especially include challenging chromatography and minimal extraction recovery, and, due to large numbers of basic amino acids and the resulting immobility of protons, resistance against collision-induced dissociation. We developed a surro-gate quantification of a CPP-lipid-conjugate relying on elimination of the lipid-part by phospholipase D digestion. Chromatograph-ic separation was only feasible with trifluoro acetic acid (TFA) based mobile phases. Ion suppression caused by TFA was reversed by post-column addition of aqueous ammonia. Efficient extraction of the surrogate peptide fragment was achieved by protein precipitation with TFA. This enabled the highly sensitive quantification of the CPP-lipid-conjugate in plasma in the low picomolar range (lower limit of quantification of 0.1 ng/mL; 34 pM). The assay was validated according to the pertinent guidelines of the FDA and EMA on bioanalytical method validation and applied to the determination of intravenous pharmacokinetics of the CPP-lipid-conjugate in Beagle dogs. The established strategy can be used as a general approach to the bioanalysis of amphiphilic lipid-conjugates and especially the TFA-based UPLC-MS/MS analysis for arginine rich peptides and other substances with challenging chromatographic characteristics.
bis(trifluoromethyl)-carborhodamines for live cell imaging
Authors: Gerstner Nels , McCann Jack , Martin Julia , Henn Katharine , Riske Kathrin , Anantakrishnan Sathvik , Graham Thomas , Darzacq Xavier , Miller Evan
Published: October 2024

Synthetic fluorophores built on a classic rhodamine scaffold are essential for modern microscopy. An attractive feature of synthetic fluorophores is their potential to access long wavelength excitation and emission profiles (>650 nm) that are difficult to achieve through genetically encoded methods like fluorescent proteins. Here, we present a new strategy to achieve excitation and emission above 650 nm: bis(trifluoromethyl)carborhodamine dyes, or BF dyes. In BF dyes, the geminal methyl groups of carborhodamines are replaced with trifluoromethyl (CF3) groups. This accomplishes two things. First, CF3 groups substantially red shift in the optical profile by over 90 nm compared to classic, oxygen-bridged rhodamine dyes, resulting in a dye framework with excitation and emission profiles >650 nm and high brightness (extinction coefficient >140,000 M-1cm-1 and fluorescent quantum yield of 33%). Second, CF3 groups render BF dyes fluorogenic, by shifting the position of the open-closed equilibrium of the colorless lactone and colored zwitterion form, resulting in up to 30-fold improvement in fluorogenicity compared to silicon-bridged rhodamines. In this paper, we present the design and computational analysis of BF dyes; synthetic studies to access over a dozen new BF dyes through a unique, late-stage functionalization strategy; spectra characterization; and applications in advanced fluorescence microscopy including no-wash intracellular labeling, functional imaging with chemigenetic indicators, and single molecule tracking in living cells. Together, this report shows that bis(trifluoromethyl)carborhodamine dyes provide a complementary approach to achieving long-wavelength, fluorogenic dyes for live cell microscopy that does not rely on dimethyl silicon rhodamines.
Accelerating Molecular Dynamics Simulations Using Socket-Based Inter-Process Communication
Authors: O. Bispo Matheus , Barbatti Mario
Published: October 2024

Molecular Dynamics (MD) simulations are essential for studying the time evolution of molecular systems. Still, their efficiency is often bottlenecked by file-based Inter-Process Communication (IPC) between MD and Electronic Structure (ES) programs. We present a socket-based IPC implementation that dramatically accelerates MD simulations, reducing computational time by over tenfold compared to traditional file-based methods. Our approach, applied to nonadiabatic molecular dynamics with the Newton-X program, eliminates disk read/write overhead, allowing for faster simulations over longer timescales. This method opens the door to more efficient high-throughput simulations, providing new opportunities for exploring complex molecular processes in real-time.
Gas-phase and model ice-surface reactions of S(1D) with water and methanol: a computational investigation and implications for cosmochemistry/astrochemistry
Authors: Giustini Andrea , Di Genova Gabriella , Skouteris Dimitrios , Ceccarelli Cecilia , Rosi Marzio , Balucani Nadia
Published: October 2024

Gas-phase reactions of atomic sulfur in its first electronically excited metastable state, S(1D), with water and methanol have been theoretically investigated to characterize their potential energy surfaces, the reaction mechanisms, and product branching fractions. According to our results, both reactions proceed with the formation of bound intermediates that, for the isolated systems, decompose into products because of the large energy content with which they are formed. The SO(a 1Δ) + H2 channel is the only open for the S(1D) + H2O reaction, while many channels are open for the S(1D) + CH3OH reaction. For the latter case, statistical estimates of the product branching fractions indicate that the main channels are those leading to CH2OH + SH, H2CO + H2S, H2CS + H2O, and CH3 + HSO. The mechanism of the related O(1D) + CH3SH reaction has also been unveiled. Since the reaction intermediates can be stabilized by energy loss to surrounding species on ice or in liquid water, to gain some insight into the possible effects of water molecules we have also analyzed how the two reactions behave when four additional water molecules are added. The conclusion is that the initial intermediates formed by the insertion or addition mechanism − namely HOSH (hydrogen thioperoxide) and H2OS for S(1D) + H2O and CH2OHSH (mercaptomethanol), CH4OS and CH3OSH (methyl thioperoxide) for S(1D) + CH3OH, as well as CH3SOH (methyl sulfenic acid) for O(1D) + CH3SH − will probably be stabilized by the interaction with the additional water molecules. Our results can help in understanding sulfur chemistry in space, especially in the case of comets. On one side, the S(1D) + H2O gas-phase reaction could account for the additional SO source necessary to explain the observed distribution of this species obtained by using the Plateau de Bure interferometer of Institut de Radioastronomie Millim´etrique (IRAM) for the Hale Bopp comet. On the other side, some of the S/O-containing molecules identified by ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) during the enhanced dust emission events of the 67/P comet (e.g. species with gross formula HSO, H2SO, and CH4OS) could be the results of the chemistry occurring on ice that we have exposed in this work.
Assessment of Pollution of Sediments of Accumulative Shores of the Yarki Island (the Northern Part of Lake Baikal)
Authors:   Institute of the Earth's Crust SB RAS, Pellinen V. A. , Kovalevskaia A. I. ,   M. V. Lomonosov Moscow State University
Published: October 2024

The article presents the current ecological and geochemical condition of sediments of accumulative shores of the Yarki Island in the northern part of Lake Baikal. Sediment samples were taken at key pointes. The tasks of this work also included the determination of the chemical composition of the deposits of the Yarki Island with using the XRF method and the assessment of their pollution. It has been established that in the considered coastal zone of the Yarki bar, the sediments are contaminated with heavy metals such as strontium, lead, and in some places arsenic, which probably have an anthropogenic source of their entry into the bar’s sediments. It indicates the possibility of smaller particles to sorb some elements. The distribution of chemical elements along the Yarki Island is uneven. There is no dependence between the indicator values and the location of the points in relation to the channels. It indicates a minimal effect of the channels on the condition of the sediments of the Yarki Island. Probably the increased content of chemical elements in some sediment sampling points is associated with the location of recreational zones in these areas.
MEDIA DISCOURSE OF «HATE SPEECH» IN DIGITAL COMMUNICATION: CASES OF SOCIAL MEDIA
Authors:   AL-FARABI KAZAKH NATIONAL UNIVERSITY, Ormakhanova Yenlik
Published: October 2024

The article is devoted to the phenomenon of implementation of traditional forms of “hate speech” on the social networks such as Facebook and Instagram. In particular, the content and stylistics of texts containing signs of “hate speech”, the aspects of framework normative documents and the main con- cepts of verbal aggression in electronic communication are analyzed. Moreover, the concept and media discourse of “hate speech” are extrapolated to form a basic tool for building a personal brand, increas- ing loyalty on social networks through negativity, condemnation, slanderous or aggressive statements against opponents. The purpose of the study is to map the negative factors of the impact of modern socially oriented content on the stylistic and linguistic presentation in the social media texts. The author also attempted to consider the incentive motives of these phenomena and counteraction measures for the escalation of “hate speech” on the Internet. The author puts forward the idea of the need for a scientific understanding of the legal nature of “hate speech”, which includes several controversial aspects of the contraposition: the right to freedom of opinion is not/is the basis for choosing any (even aggressive or hateful) forms of expression of these opinions. The practical significance and value of the work lies in the focus on improving communication tech- nologies for monitoring and analyzing social media and systematizing available information. The author notes the need for technological strengthening of tools and methods for tracking hate speech on social networks, and proposes a discussion on defining criteria for assessing the aggression level of hate speech and its prevalence on the global network. The research methodology is based on the use of comparative, textual and linguistic analyzes of precedent electronic media texts containing signs of “hate speech”. The results of the study substanti- ate the need for a prompt response to the dynamic increase of hateful rhetoric by society and the state, strengthening methods of legal counteraction and ethical regulation, as well as increasing media and information literacy of the population. From the point of view of professionalizing the blogosphere, it is reasonable to use mediation technologies for conflict resolution, promote the concept of a respectful interactive environment and strengthen counteraction measures for “hate speech” in social networks.
SPORTS CLUB LOYALTY: GENERAL AND AGE-RELATED ANALYSIS. AN EXAMPLE FROM RECREATIONAL RIDERS IN RIDING SCHOOL
Authors: Vial Céline , Eslan Camille , Costa Sandrine
Published: October 2024

Objective: The objective of this study is to investigate the impact of age on sporting club loyalty, focusing on horse riding in France.
 
Theoretical Framework: Using a consumer behavior marketing approach, this study provides an understanding of the relationships and influence between the constructs of loyalty, satisfaction, switching barriers, affective commitment to the group of friends and community commitment.
 
Method: A multigroup SEM was used to provide a global understanding. The Data collection was carried out through on online survey amongst 615 respondents in France.
 
Results and Discussion: Whatever the age is, the results confirm the classical influence of satisfaction on loyalty and highlight the significant influence of riding teachers on customer loyalty to riding schools. The relationships between the other constructs differ by age with different factors influencing satisfaction and loyalty. Younger riders’ loyalty relies more on teacher linkage, while older riders consider a more global environment, including switching barriers and commitments.
 
Research Implications: The practical and theoretical implications of this research are discussed, providing insights into how the results can be applied or influence practices in the field of sport management. These implications could encompass equestrian activities and sports businesses.
 
Originality/Value: This study contributes to the literature by showing the differences or correlations between segments of recreational riders according to their loyalty to their riding club. Thus, adapting marketing and management strategies according to the age of recreational riders is essential to improve loyalty according to its main drivers.
ANALYZING THE IMPACT OF FREIGHT TRANSPORT, GDP, AND PESO – BAHT EXCHANGE RATE ON PHILIPPINE TRADE IN DESICCATED COCONUT USING THE GRAVITY MODEL OF INTERNATIONAL TRADE
Authors: Prado Joshua Lapitan Del , Manfoste John Maxene Gonzales , Rosete Marie Antoinette Lukban
Published: October 2024

Objective: The objective of this study is to investigate the impact of freight transport, Gross Domestic Product (GDP), and the Peso-Baht exchange rate on the trade of desiccated coconut between the Philippines and Thailand, utilizing the Gravity Model of International Trade. The primary aim is to understand the significant factors influencing the trade flow and to identify areas for improvement in international competitiveness.
 
Theoretical Framework: The research is grounded in international trade theories, focusing on the Gravity Model, which emphasizes the roles of economic mass and geographical distance in determining trade flows.
 
Method: This study made use of the ADF - Unit Root Test, Durbin – Watson Test, Jarque – Bera Test, Variance Inflationary Factor (VIF), Chow Breakpoint Test, Ramsey’s RESET, and Johansen Cointegration, to test the relationship between variables.
 
Results and Discussion: The results of this study highlights the positive, yet insignificant effect of Thailand, and Philippines’ GDP on the trade in desiccated coconut. The exchange rate, and freight transport negatively impacts the trade, however, it is notable that only freight transport having a significant effect.
 
Research Implications: The study provides insights into the logistical and economic challenges in the desiccated coconut trade, suggesting that addressing transportation inefficiencies and stabilizing exchange rates could enhance trade performance.
 
Originality/Value: This study contributes to the literature by applying an innovative approach to desiccated coconut, revealing how logistical inefficiencies and economic variables affect trade flows and influence policy decisions. This research aids in enhancing trade efficiency between agricultural-exporting nations like the Philippines and Thailand.
INSPECTION AS A TOOL FOR EVALUATION AND IMPROVING THE QUALITY OF EDUCATION
Authors:   Shumen University ‘Bishop Konstantin Preslavski’, Shumen, Georgieva Snezhanka
Published: October 2024

The article presents a comparative analysis of the quality of education assessed by the National Inspectorate of Education in schools from the administrative district of Shumen. The research compares the grades received by schools in two periods – during the 2021/2022 academic year and 2023/2024. The demonstrated strengths in the activity of educational institutions are summarized and analyzed, as well as aspects of the educational process, management and institutional environment that need improvement. Based on the research, typical shortcomings in the work of the schools were identified. Conclusions are made about the possible ways and approaches to increase the quality of education, including competence-oriented training, transparent and autonomous management and improvement of the educational environment.