bluuebunny/crossref_metadata_2025 huggingface dataset:
Prison Penalty In Providing A Determination Effect For Criminal Actions Of Corruption
Authors: Tamza Fristia Berdian
Published: November 2022

The case of corruption as a phenomenon of deviation from social, cultural and state life has many scientists and philosophers study and criticize it. One of the world's famous philosophers is Aristotle, who formulated what he calls moral corruption. Moral corruption refers to various forms of the constitution that have deviated so that the regime's rulers are included in the democratic system where by they are no longer led by law, but also on the other hand no longer serv themselves. The problem in this research is the Effectiveness of Imprisonment for Criminal Acts of Corruption, and Does Imprisonment Can Have a Deterrent Effect on Perpetrators of Criminal Acts of Corruption? This paper is a normative legal research. This normative legal research method is used because the approach in this paper is carried out by using a case approach and a statute approach.
The prison sentence is threatened for someone who has committed a crime. Imprisonment: consists of life imprisonment and temporary imprisonment or imprisonment for a specific time. The temporary prison sentence is a minimum of one day and a maximum of fifteen years. However, temporary imprisonment may be imposed for twenty years if the crime committed by a person is punishable by death or life imprisonment or is threatened with imprisonment of 20 (twenty) years if there is a combination of several criminal acts (same lop) the perpetrators of criminal acts of corruption deserve death penalty, as such being given the death penalty will provide a deterrent effect and also be a lesson for others not to do the same thing (corruption). Almost no judges generally impose the death penalty because it is associated with aggravating or mitigating reasons. The mitigating factor is far more dominant regarding the highest sentence limit, education, and others.
Efficacy of phototrophic bacterial feed supplementation on economic traits and disease resistance in mulberry silkworm, Bombyx mori (Lepidoptera: Bombycidae)
Authors: RAHUL Kamidi , ANIL Pappachan , POOJA Makwana , MIHIR Rabha , VANKADARA Sivaprasad
Published: November 2022

Sericulture, often known as silk farming is the practice of rearing silkworms for production of raw silk. One of the major impediments faced by the sericulture community is the silkworm diseases that cause significant crop losses. In the present study, the efficacy of phototrophic bacteria as feed supplements in improving the economic traits as well as disease resistance in mulberry silkworm, Bombyx mori L. was assessed. A total of three phototrophic bacteria were isolated and identified as belonging to the genera Marichromatium, Rhodobacter and Rhodopseudomonas based on 16S rRNA gene sequencing analysis. Their morphological, physiological and biochemical characters were studied, grown under ambient conditions and biomass was harvested. Mulberry fortified with the aforementioned phototrophic bacteria in solitude and combinations at varying concentrations (0.5, 1, 2 and 5%) were found to be innocuous to the mulberry silkworm. The best results were observed when mulberry leaf was supplemented with Rhodopseudomonas sp. at 2% concentration which improved survival, cocoon weight, shell weight, shell%, filament length and non-breakable filament length by 5.18, 0.27, 3.86, 3.5, 1.5 and 1.2%, respectively under normal rearing conditions. Under Staphylococcus sp. infected conditions, the aforesaid diet also enhanced survival in silkworms by 16%. On the other hand, the same diet didn’t exhibit any discernible influence on survival against fungal, viral, or microsporidian infections in silkworm.
First record of Camarochilus confusus (Heteroptera: Pachynomidae) from Argentina, the second pachynomid and first Pachynominae registered for the country
Authors: MELO María Cecilia , DELLAPÉ Pablo M.
Published: November 2022

Fieldwork in two protected areas from northeastern Argentina (P.N. El Impenetrable in Chaco Province, and the P.N. Rio Pilcomayo in Formosa Province) exploring the Heteroptea fauna, resulted in the discovery of a Camarochilus confusus Harris 1930 male that was collected by sweeping the vegetation. The species belongs to the subfamily Pachynominae, representing the first record of the group in the country. Aphelonotus simplus Uhler 1894 (Aphelonotinae), was also collected using light traps, confirming its occurrence in the Chaco ecoregions in Argentina.
The Effect of Using Spaced Learning Repetition Method on Iraqi Islamic School Students' Achievement in English Language
Authors: Mustafa AL-Okiedy Omar Mahmood
Published: November 2022

The current study aims to investigate the effect of using spaced learning repetition method on Iraqi Islamic school students' achievement in  English language. The aim of the study is supposed to be achieved through verifying its hypothesis. The sample of the study consists of twenty EFL Islamic school students who are spread into both groups, the experimental groups and control .The experimental group has been taught the English reading comprehension(The Prophet of Allah unit seven and eight) by using spaced learning repetition method ,while the control group has been taught the same material by using their current method. A posttest has been applied and conducted to the both groups. The required data are collected and analysed statistically. The gained findings show that the mean scores of students' achievement of the experimental group in the posttest are better than that of the control group. This means that the investigated method has an efficient effect on Iraqi Islamic school learners' achievement language of English.
Biotelemetric Experiment in the Radiotelegraphic Bureau of the Maritime Department (1912). A New Episode from the History of the Development of Russian Science
Authors: Vladzymyrskyy Anton Vyacheslavovich
Published: November 2022

The minutes of the meeting of the Society of Marine Physicians in St. Petersburg dated October 30, 1912, which describes an experiment on the transmission of biomedical data via telecommunications, are published. The head of the workshop of the Radiotelegraph depot A.K. Nikiforov developed a device for remote transmission of the sound picture of the heart, using his own designs of amplifiers and microphones. The experiment was conducted with the participation of doctor A.G. Makarov. The results indicated insufficient broadcast quality and required technical refinement of the device. Comparison with the effectiveness of similar experiments in other countries shows that in the studied period of time, the general level of technical development did not fundamentally allow solving the problem of high-quality transmission of biomedical data over a distance. The fact of the experiment revealed by the author, which occurred against the background of institutionalization of scientific research in the Radiotelegraph Depot, is extremely important from the point of view of systematization of the history of domestic scientific research in the field of biotelemetry. When studying archival materials, the processes of institutionalization of scientific work in the Radiotelegraph Depot were revealed, including regulatory support, creation of organizational structures, distribution of goals and objectives, financing, and resource provision. The formal structuring of scientific activity formed the context for scaling research into other fields of knowledge, which created the basis for A.K. Nikiforov's scientific and design activities in the field of biomedicine. The scientist-engineer made a contribution to the accumulation of knowledge and the future formation of dynamic biotelemetry as a separate scientific direction.
Exhibition activity of the Palekh lacquer miniature craft (1945-1989)
Authors: Lavrov Dmitrii Evgen'evich
Published: November 2022

The study is a continuation of the article "Exhibition activity of the Palekh lacquer miniature craft (1923-1939)", published in the scientific journal "Man and Culture". The subject of the proposed work is an analysis of the exhibition activity of the Palekh lacquer craft in the post-war period, limited to the second half of the 1940s and the end of the 1980s. The purpose of the article is to use historical, typological and structural research methods, as well as a historical and systematic approach, to show the specifics of this period in the history of the exhibition activity of the Palekh craft. Emphasizing the continuity of the exhibition activities of the 1940s - 1980s with the pre–war period, the author at the same time points out the new features that appear in the exhibition practices of the craft in the post-war period.   The scientific novelty of the research consists in the fact that the author analyzes the most important art shows of the Soviet Union, where the products of the Palekh lacquer miniature were exhibited in the 1940s – 1980s. The article pays special attention to the activities of the State Museum of Palekh Art, which after its opening in 1935 became an important exhibition center for lacquer craft products, personal, retrospective, thematic and traveling exhibitions are considered. The main conclusion of the article is the substantiation of the importance of the considered topic for understanding the public recognition and fame that the Palekh lacquer miniature craft acquired in the late Soviet period, as well as in the post-Soviet period.
Constructive realism in the construction of artistic images of fine art in the context of the creation of symbolic meanings
Authors: Kalina Natalia Dmitrievna
Published: November 2022

The object of the study is the symbolic and allegorical meanings of artistic images of fine art, built in the unity of the diverse, based on the principle of the relationship between the real and the conditional. The subject of the study is a comparison of the methods of metaphysical and constructive realism in creating aesthetically expressive forms of artistic images expressing symbolic meanings. The article systematizes the methods of creating artistic images in constructive realism: typification, stylization, artistic and theoretical generalizations, analysis, synthesis, application of constructive ideas of combining parts of the whole, geometric generalization of form in the construction of the spatial structure of the object, artistic interpretations. The main method of image research is the analysis of visual contexts of the application of the concept of methods and other means of constructing artistic images. The novelty of the article lies in constructive realism in creating deeper symbolic meanings than the generally accepted forms of realism convey. With constructive realism, aesthetically expressive images are created in the unity of the heterogeneous and do not distort the conventional meanings. In the differentiation of means and integration of image layers, the image represents a single symbolic meaning. As a result of the analysis of constructive realism, four regular processes of building the unity of the diverse in the form and content of artistic images have been revealed. The conclusion is that constructive realism to the construction of artistic images has practical significance. The images are characterized by aesthetic expressiveness, this attracts the attention of the audience. In expression through the form of symbolic meanings, images acquire the potential of visual communication with people.
Distributed Governance of Medical AI
Authors: Price W. Nicholson
Published: November 2022

Artificial intelligence (AI) has the potential to democratize expertise in medicine, bring expertise previously limited to specialists to a variety of health-care settings. But AI can easily falter, and making sure that AI works well across that variety of settings is a challenging task. Centralized governance, such as review by the Food and Drug Administration, can only do so much, since system performance will depend on the particular health-care setting and how the AI system is integrated into setting-specific clinical workflows. This Essay presents the need for distributed governance, where some oversight tasks are undertaken in localized settings. It points out the resource-based challenges of such governance and offers policy suggestions to ease the burden.
Various techniques for marking patch test sites
Authors: Prabha Neel , Yadav Hitesh
Published: November 2022

Patch test helps in identifying the allergen causing allergic contact dermatitis. Proper identification of the site of individual patch test allergen is very important for identifying the positive allergen. In this article, various techniques for markings patch test sites are discussed.
FEATURES OF PROJECT FINANCE AND ITS INFLUENCE ON THE ORGANIZATIONAL STRUCTURE OF PROJECTS
Authors:   Lviv Polytechnic National University, Ilchuk Pavlo , Derkutsa Olha ,   Lviv Polytechnic National University, Hudash Svitlana ,   Lviv Polytechnic National University
Published: November 2022

The article examines the impact of project financing on the development of projects throughout their life cycle in general, and its specific impact on the organizational structure of projects, in particular. Based on the statement that financial planning in projects is an important component of the design phase, while project financing is an integral element of all subsequent phases of the project life cycle, the need to consider the impact of the type of project financing on the model of the organizational structure of projects is substantiated. It is separately substantiated that the type of project financing will determine the general model of the organizational structure of the projects. It is in connection with the identification of such an influence that the essence of project financing is specified in the article and the main types (mechanisms) of project financing are investigated and their strengths and weaknesses are substantiated. On the basis of empirical data, it has been proven that the financing of economic activity in the form of project financing is extremely common in the world economy, and in certain types of economic activity it can be considered a priority form of financing. It has also been proven that the volume of project financing in the world economy is constantly growing, in particular, in the European Union during the last 6 years, such growth amounted to about 100%. Interrelationships between the type of project financing and models of the organizational structure of projects were analyzed, and certain features of the formation of the organizational structure of projects were identified depending on the selected type of project financing. It has been proven that it is the partnership type of project financing under which the SPV (SPE) is created that has the greatest opportunities for representing the interests of project stakeholders precisely during the formation of the organizational structure of project management, and also has the widest range of opportunities for attracting project financing from various sources.
DEVELOPMENT OF THE SYSTEM OF FINANCIAL SECURITY OF BUSINESS ENTITIES IN THE AGRICULTURAL INDUSTRY
Authors:   Kyiv National University of Technologies and Design, Soroka Mariia , Tarasenko Iryna ,   Kyiv National University of Technologies and Design, Kovalenko Dmytro ,   Kyiv National University of Technologies and Design
Published: November 2022

The agricultural sector of the economy is the leading one in the economy of Ukraine. The financial security of agro-industrial enterprises as a component of the country's financial security is one of the strategic directions of the development of the economic policy of Ukraine, since it is the development of the agrarian sector of the economy that is able to ensure food security not only in our country, but also in the world. Among scientists engaged in the study and research of issues related to the agricultural sector, discussions often arise about the promotion of financial security to the effective development of agricultural entrepreneurship, and therefore, the provision of general – food, ecological, social and economic – security of the country. These discussions are due to the complexity and peculiarities of financial relations in this field. Therefore, maintaining the appropriate level of financial security of enterprises in the agricultural sector is one of the primary tasks of the development of the economy of Ukraine. The article is devoted to the study of the system of financialsecurity of agro- industrial enterprises and the outline of the main directions of its evaluation.
CURRENT ISSUES OF DETERMINING SUBJECTIVE SIGNS OF REMAINING IN DANGER
Authors:   Dnipropetrovsk State University of Internal Affairs, Hrytenko Oksana
Published: November 2022

The article examines topical issues of establishing subjective signs for leaving in danger, namely the essence, interpretation and definition of subjective signs for qualification under Art. 135 of the Criminal Code of Ukraine. Such subjective signs of Art. 135 of the Criminal Code of Ukraine, as guilt and the subject of a criminal offense. It has been established that among the complex issues that arise in law enforcement activities in the qualification of Art. 135 of the Criminal Code of Ukraine there is the establishment of the second alternative sign of this norm - putting the victim in a state of danger to life and health and leaving him without help, as well as the correct interpretation of the expression of the legislator "he himself put the victim in a state of danger to life", when the issue is resolved through mutual fault . It is proved that among the topical issues of subjective signs of being left in danger, there are certain difficulties in the established forms of guilt (intention or negligence) in each specific case. Attention is drawn to such topical issues in the qualification of Art. 135 of the Criminal Code of Ukraine, as establishing the type of subject of a criminal offense, especially when it is necessary to determine the type of subject where the victim was left in a dangerous condition caused by a traffic accident. An analysis of the relevant issue provided grounds to assert that the subjects of being left in danger can be not only persons obliged to take care of the victim, but also those who are obliged to provide the necessary assistance to persons in a dangerous state, based on their profession, the requirements of regulatory enactments. It is also essential to determine the types of subjects of a criminal offense under Art. 135 of the Criminal Code of Ukraine, in a situation in which the victim was left in a dangerous condition caused by a traffic accident, since it is the definition of a specific type of subject that affects the final qualification.
SOME ISSUES OF THE SIMPLIFIED LABOR REGULATION REGIME
Authors:   Yaroslav Mudriy National Law University, Svichkarova Yaroslava , Zavialov Yehor ,   Yaroslav Mudriy National Law University
Published: November 2022

The consequences of the full-scale invasion of the Russian Federation on the territory of Ukraine on February 24, 2022 will be felt for a long time: families were separated and relocated; the development of human potential was violated, the cultural heritage was destroyed, and the positive trajectory of economic development changed to a negative one. In these harsh conditions, labor legislation was adapted to the conditions of martial law. Thus, at the beginning of March 2022, the Law of Ukraine No. 2136-IX "On the organization of labor relations under martial law" was adopted. During the period of martial law in our country, the norms stipulated by the Law of Ukraine No. 2434-IX "On Amendments to Certain Legislative Acts of Ukraine on Simplifying the Regulation of Labor Relations in the Field of Small and Medium-Sized Enterprises and Reducing the Administrative Burden on Entrepreneurial Activity", adopted on 19 July 2022. This Law proposed rather bold, as for Ukrainian labor law, ideas called "simplified mode of regulation of labor relations". The article analyzes some provisions of Chapter III-B of the Code of Labor Laws of Ukraine. It is noted that in many aspects such norms contradict other provisions of the Labor Code of Ukraine, the Constitution of Ukraine and international legal acts. It was determined that on the way to full membership in the European Union, domestic legislation must meet the basic requirements of international legal acts.
LEGAL SUPPORT OF INTERACTION OF THE MINISTRY OF DEFENSE OF UKRAINE WITH OTHER SUBJECTS IN THE SYSTEM OF DEMOCRATIC CIVIL CONTROL
Authors:   Military Institute of Taras Shevchenko National University of Kyiv, Koropatnik Ihor , Karelin Vladyslav ,   Military Institute of Taras Shevchenko National University of Kyiv, Lytvyn Nataliia ,   Scientific and Educational Institute of Law of the Taras Shevchenko National University of Kyiv
Published: November 2022

The article defines that legal provision is a set of legal norms and the practice of their implementation, united by the purpose and principles of legal regulation. Such a structure makes it possible to adjust the legal norm in a timely manner from the point of view of its effectiveness or ineffectiveness in certain political, economic, and social conditions of the life of society and the state. Arguments are given that the role of legal support in the effective functioning of the security and defense sector in the conditions of full-scale Russian armed aggression is manifested in three main vectors. First, it is the creation of favorable legal conditions for the strengthening and development of the Armed Forces of Ukraine, other military formations, law enforcement and intelligence agencies, which directly provide repulsion to the enemy's armed aggression. Secondly, it is the development of legal foundations for ensuring public order, protection of human and citizen rights, bringing those guilty of criminal crimes to legal responsibility during the de-occupation of temporarily occupied Ukrainian territories. Thirdly, it is the reduction of the destructive influence of corruption risks on legal relations in the security and defense sector. The article substantiates that the legal principles of interaction of the defense department with other subjects of the specified type of control are based on legal acts of various nature, which are classified according to the criterion of the content of legal norms. It was concluded that the legal support for the interaction of the Ministry of Defense of Ukraine with other subjects in the system of democratic civilian control in the legal aspect is a set of legislative and subordinate legal acts, which define the legal status of subjects of control, their mission, purpose, tasks, functions, features of the implementation of powers and responsibilities. As a management phenomenon, the researched type of legal support includes multidirectional management influences and organizational forms of their implementation, which allow for productive law enforcement activities aimed at determining and correcting the current state of objects of democratic civil control.
ANALYSIS OF CHANGES TO THE LAWS OF UKRAINE UNDER THE CONDITIONS OF MARITAL LAW IN THE FIELD OF ENFORCEMENT OF COURT DECISIONS. FORECASTED CONSEQUENCES OF THESE CHANGES FOR THE ECONOMIC RECOVERY OF THE STATE
Authors:   Kharkiv National University of Internal Affairs, Kupriyanova Anastasiia
Published: November 2022

The article is a study of such levers of influence and balancing of the state budget as a sphere of execution of court decisions, which belongs to the direction of the sphere of justice. Legal protection occupies a leading place in modern society. In Ukraine, the European model of full-fledged enforcement of court decisions is constantly developing. Today, when the eight-year war with the Russian aggressor continues, Ukraine is on the path of major changes and reforms, which are aimed at increasing the effective operation of all state authorities under martial law, including the judicial branch, which carries out its activities by resolving legal conflicts between citizens, authorities and organizations. The experience of the European Court of Human Rights, which introduced a special pilot decision procedure to speed up the consideration of similar cases, is mentioned. Despite the emergence of many problematic issues of the functioning of the judicial system and the execution of court decisions in the conditions of a full-scale invasion of Russia, the law-making process in Ukraine continues, the leading task of which is to improve, increase efficiency and expand opportunities for the implementation of judicial proceedings. In this regard, quite a large number of draft laws have been proposed and already implemented, the purpose of which is to simplify and improve the conditions of activity of pre-trial investigation bodies, judicial spectrum of actions and executive bodies and services. The article also analyzes the Law of Ukraine "On Executive Proceedings", the Law of Ukraine "On Amendments to Certain Laws of Ukraine Regarding the Activity of Private Executors and Enforcement of Court Decisions, Decisions of Other Bodies (Officials) During the Period of Martial Law", the Law of Ukraine "On Bodies and Persons Carrying Out Enforcement of Court Decisions and Decisions of Other Bodies", the draft Law of Ukraine "On Amendments to Certain Legislative Acts on Improving the Mechanism of Judicial Control over the Execution of Court Decisions and the Procedure for Establishing or Changing the Method of Execution of Court Decisions". At the same time, approaches to judicial control really need changes, so that it becomes one of the effective means of full and timely execution of court decisions, which is a certain step towards the economic recovery of Ukraine after the introduction of martial law and Russian aggressive activity towards our country.
STRUCTURE OF EXECUTIVE GOVERNMENT BODIES AND LOCAL GOVERNMENT BODIES COMPETENCES UNDER THE CONDITIONS OF DECENTRALIZATION
Authors:   Educational and Scientific Institute of Public Administration of the Lviv Polytechnic National University, Deneha Vitalii
Published: November 2022

The structure of competencies of the executive power bodies and local self-government bodies in the conditions of decentralization has been studied. It was found that the demarcation of the subjects of management, powers, and competencies of local self-government bodies and local state authorities in Ukraine acquires not only a legal but also a political character. It has been established that there is a direct dialectical relationship between competence and decentralization at the national level and competence and decentralization at the level of local self-government. In such a chain of procedural objectification, the key term will be the competence of local self-government bodies, as a system of authorized subjects - authorized bodies and self-governing subjects, as well as structures functioning at the local social level, formed by society itself to satisfy the collective, group and individual needs of its members. It is substantiated that the application of the principle of subsidiarity determines the effective formation of the competence of local self-government bodies. Guided by this principle, social problems are solved at the lowest or most decentralized (farthest from the center) level, at which it is most effective: state executive authorities should play an auxiliary (subsidiary) and not a subordinate (subordinate) role, performing only those tasks that are not can be effectively implemented at the local level.
THE STATE’S ROLE IN PROVIDING HEALTH CARE PERSONNEL OF UKRAINE TOWARDS EUROPEAN INTEGRATION
Authors:   S. Kuznets Kharkiv National University of Economics, Akhmedova Olena
Published: November 2022

The role of the state in the process of the health care system formation and provision with highly qualified personnel in the context of Ukraine’s integration into the European space has been outlined in the paper. The state support programs for the health care sector at the world and European levels, priorities for the medical education development have been analyzed. The problems of the Ukrainian health care system have been identified and suggestions regarding the transformation of the mechanism of personnel support in the field of health care by bringing medical education closer to European standards have been made.
Improvement of Potato Seeds Production in Regional AgroIndustrial Complex
Authors: Селиванова Людмила Андреевна , Васильева Наталья Витальевна
Published: November 2022

В статье обосновывается необходимость создания новой организационной структуры - регионального научного центра по производству оригинальных семян картофеля. В качестве точки роста такого центра выступает НИУ федерального уровня Ленинградский научно-исследовательский институт сельского хозяйства «Белогорка» (ЛНИИСХ «Белогорка»). Создание центра обеспечит повышение качества семян картофеля, эффективности использования ресурсного потенциала отраслевой науки, рентабельности производства семян.

The article provides evidence of the need for creating a new organisational entity - a regional research center for growing original potato seeds. As a growth point there serves Leningrad Scientific Research Institute of Agriculture Belogorka (LNIISH Belogorka). The creation of such a center will provide potato seeds quality increase, promote efficiency of the use of the sectoral science resource potential and ensure profitability of growing seeds.
Change of Priorities when Ensuring Secu rity in Arctic Zone of Russian Federation
Authors: Пудовкина Ольга Игоревна , Соломонова Валентина Николаевна , Редькина Татьяна Марковна
Published: November 2022

Актуальность статьи связана с необходимостью усиления роли Арктической зоны РФ в обеспечении безопасности страны. Авторы описывают меры по обеспечению безопасности со стороны государства в течение последних пяти лет в Арктической зоне РФ. Авторы считают, что конкретизация мер по обеспечению безопасности в Арктическом регионе должна быть направлена на развитие территории, а не на усиление политического или экономического влияния страны в мире. В статье обосновывается идея о том, что в складывающихся условиях хозяйствования необходима переориентация предпринимаемых усилий стратегического развития в Арктической зоне РФ с обеспечения безопасности как мер защитного характера на расширение партнерских отношений.
Comparative Characteristic and Features of Organization Structures for Innovations Implementation
Authors: Степаненко Дарья Александровна , Ермолина Алена Алексеевна
Published: November 2022

Предметом исследования является типология организационных структур. Работа посвящена изучению опыта построения и выбора организационной структуры, способствующей эффективному внедрению инноваций. На основе анализа адаптивных и бюрократических организационных структур, сравнения их преимуществ и недостатков в процессе внедрения инноваций, были определены структуры, наиболее удовлетворяющие признаку организационной симметричности. Сделан вывод о наличии признаков организационной симметричности в дивизиональной и матричных структурах, что делает их использование эффективным при внедрении инноваций.

We look at the typology of organizational structures. The research is dedicated to the experience of creating and choosing an organizational structure favorable for implementing innovations. By analyzing adaptive and bureaucratic organization structures and comparing their advantages and disadvantages, we distinguish the structures that are the closest to organizational symmetry. We make a conclusion that organizational symmetry can be seen in divisional and matrix structures, which determines their effectiveness when implementing innovations.
The hydrothiolation of TIPS-CΞC-SF5 – Charting the chemical space of beta-SF5 vinyl sulfides
Authors: Kucher Hannes , Wenzel Jonas Oliver , Rombach David
Published: November 2022

The pentafluorosulfanyl group is suggested to be a promising candidate adding to the toolbox of emerging fluorinated motifs. While the synthesis of non-aromatic SF5 bulding blocks generally requires on-site fluorination or pentafluorosulfanylation steps employing toxic and/or gaseous reagents, downstream processing of commercially available prefunctionalized molecules is proposed as an alternative strategy to allow access to this motif by less specialized laboratories. Herein, we report a benign bench-top protocol for the synthesis of Z-configured beta-pentafluorosulfanylated vinyl sulfides in good to excellent yields with excellent Z-diasteroselectivity and broad functional group tolerance. This general method exploits an in-situ protodesilylation-hydrothiolation sequence of commercially available liquid and high-boiling TIPS-CΞC-SF5 (TASP). This so far uncharted class of compounds was analyzed by means of NMR-spectroscopy as well as SC-XRD. Furthermore, we suggest the reaction to proceed via a kinetically controlled closed-shell reaction pathway corroborated by in-silico experiments.
Asymmetric Potential Barrier Lowering Promotes Photocatalytic Nonoxidative Dehydrogenation of Anhydrous Methanol
Authors: Jia Kun , Wei Xuhui , Xu Yang , Wang Zhijian , Chen Jiazang
Published: November 2022

Photocatalytic nonoxidative dehydrogenation of anhydrous methanol can be a promising approach to producing formaldehyde and hydrogen as it can avoid catalyst degradation occurred at high temperature in conventional catalysis. To facilitate the rate-determining step, we propose to lower the barrier height for semiconductor-cocatalyst interfacial electron transfer by solution acidity modulating, which shifts electroreduction potential and inherently lowers the interface conduction band position. Since this measure does not change the surface conduction band position, the increase in protons does not aggravate leakage of electron from semiconductor. The resulted asymmetric potential barrier lowering endows photocatalyst with larger driving force for enhancing utilization of photogenerated charge carriers. In our demonstrated reaction, a quantum yield of 89.9 % with formaldehyde selectivity of 95.5 % can be realized.
The Contribution of Hyperconjugation and Inductive Effects to the Pseudo-Anomeric Effect in 4-Substituted Methoxycyclohexanes
Authors: Piscelli Bruno , O'Hagan David , Cormanich Rodrigo
Published: November 2022

The importance of electrostatic non-conventional hydrogen bonds (NCHBs) to the pseudo-anomeric effect of 4-substituted methoxycyclohexanes is evaluated using theory (NBO) to deconvolute electrostatic from other contributing effects. There is an interesting interplay between σCH → σ*CX hyperconjugation and the electropositive charge on the 3,5-axial hydrogens (Hax). In essence better σ*CX (or 𝜋*CO) acceptors increase the charge on 3,5-CHax, which in turn strengthens Cδ⁺Hax···δ⁻OMe NCHB interactions.
Lessons for Oral Bioavailability: How Conformationally Flexible Cyclic Peptides Enter and Cross Lipid Membranes
Authors: Linker Stephanie M. , Schellhaas Christian , Kamenik Anna S. , Roth Hans-Joerg , Fouche Marianne , Rodde Stephane , Riniker Sereina
Published: November 2022

Cyclic peptides are able to extend the druggable space of pharmaceutical targets, due to their size, conformational behavior, and high proportion of hydrogen bond donors and acceptors. However, for the same reasons, they often suffer from poor membrane permeation and thus low oral bioavailability. As permeability assays do not allow to monitor the pathway and behavior of cyclic peptides on their “journey” trough lipid membranes, little is known about the underlying permeation process, which poses a major obstacle for their rational design. Here, we use molecular dynamics (MD) simulations as a computational microscope to uncover how large and conformationally flexible cyclic peptides enter and cross a lipid bilayer. In a first step, we performed unbiased MD simulations to elucidate the permeation pathway. Subsequently, this pathway knowledge was utilized to seed biased simulations to further enrich for permeation events. Based on our simulations, we show how specific side-chain residues can act as ’molecular anchors’, which establish the first contact between the peptides and the membrane, and consequently enable membrane insertion. Inside the membrane, the cyclic peptides are positioned directly between the polar headgroup and the apolar tail region, where they are subjected to a unique polar/apolar interface environment. In this environment, the cyclic peptides show a preference for one of two distinct orientations. We observe that only one of these orientations allows the formation of the permeable ’closed’ conformation, and only in this ’closed’ conformation the cyclic peptides can cross from the upper to the lower membrane leaflet, which again requires a unique anchoring and flipping mechanism. Our findings provide atomistic insights into the permeation process of flexible cyclic peptides and reveal unique design considerations for each step of the process.
HUB: A method to model and extract the distribution of ice nucleation temperatures from drop-freezing experiments
Authors: de Almeida Ribeiro Ingrid , Meister Konrad , Molinero Valeria
Published: November 2022

The heterogeneous nucleation of ice is an important atmospheric process facilitated by a wide range of aerosols. Drop-freezing experiments are key for the determination of the ice nucleation activity of biotic and abiotic ice nucleators (INs). The results of these experiments are reported as the fraction of frozen droplets f_ice (T) as a function of decreasing temperature, and the corresponding cumulative freezing spectra N_m (T) computed using Vali’s methodology. The differential freezing spectrum n_m (T) is in principle a direct measure of the underlying distribution of heterogeneous ice nucleation temperatures P_u (T) in the sample. However, N_m (T) can be noisy, resulting in a differential form n_m (T) that is challenging to interpret. Furthermore, there is no rigorous statistical analysis of how many droplets and dilutions are needed to obtain a well-converged n_m (T) that represents the underlying distribution P_u (T). Here, we present the “Heterogeneous Underlying-based” (HUB) method and associated Python codes that model (HUB-forward code) and interpret (HUB-backward code) the results of drop-freezing experiments. HUB-forward is the first available code that predicts f_ice (T) and N_m (T) from a proposed distribution P_u (T) of IN temperatures, allowing its users to test hypotheses regarding the role of subpopulations of nuclei in freezing spectra, and providing a guide for a more efficient collection of freezing data. HUB-backward uses a stochastic optimization method to compute n_m (T) from either N_m (T) or f_ice (T). The differential spectrum computed with HUB-backward is an analytical function that can be used to reveal and characterize the underlying number of IN subpopulations of complex biological samples (ice nucleating bacteria, fungi and pollen), and quantify the dependence of their subpopulations on environmental variables. By delivering a way to compute the differential spectrum from drop freezing data, and vice-versa, the HUB-forward and HUB-backward codes provide a hub between experiments and interpretative physical quantities that can be analysed with kinetic models and nucleation theory.
Catalytic C–H Alumination of Thiophenes: DFT Predictions and Experimental Verification
Authors: Zhang Linxing , Kaukver Siim , McMullen Jacob , White Andrew , Crimmin Mark
Published: November 2022

A computational model for the palladium-catalysed C–H functionalisation of thiophenes with aluminium hydride reagents has been developed. This model predicts metalation should occur exclusively at the 2-position of the heterocycle. While related 2-metallated furans are known to undergo a ring-expansion reactions, further calculations suggest that the thiophene-derived organoaluminium compounds should be both kinetically and thermodynamically stable with respect to ring-opening. This model is supported by experimental data. Selective C–H alumination of thiophene, 2-methylthiophene, 2-methoxythiophene, and benzothiophene was achieved using [Pd(PCy3)2] as a catalyst with loadings as low as 0.02 mol%. Even under extremely forcing conditions (200 ºC) there was no evidence for a ring-opening event. The differences in selectivity between furan and thiophene systems are rationalised in terms of the stabilisation of a key intermediate (and transition state) in the pathway for furan ring opening by a strong dative O–Al interaction.
The Perfluoro Cage Effect: A Search For Electron-Encapsulating Molecules
Authors: Ghosh Abhik , Conradie Jeanet
Published: November 2022

Quantum chemical calculations have for some time predicted that perfluorinated polyhedral organic molecules should exhibit a low-energy LUMO consisting av the overlapping inward-pointing lobes of the C-F * orbitals. Accordingly, they should be able to encapsulate an electron within the interior of their cavities. Inspired by the recent confirmation of this prediction for octafluorocubane, we have sought to identify additional perfluorinated cage molecules capable of this remarkable behavior, which we refer to as the perfluoro cage effect (PCE). Using DFT calculations with multiple well-tested exchange-correlation functionals and large STO-QZ4P basis sets, we have successfully identified several systems including [n]prismanes (n = 3-6), [n]asteranes (n = 3-5), twistane, and two norbornadiene dimer cages that clearly exhibit the PCE. In other words, they exhibit a low-energy LUMO belonging to the total symmetric irrep of the point group in question and adiabatic electron affinities ranging from somewhat under 1 eV to over 2 eV. A pronounced size effect appears to hold, with larger cages exhibiting higher EAs. The largest adiabatic EAs, well over 3 eV, are predicted for perfluorinated dodecahedrane and C60. In contrast, the PCE is barely discernible for perfluorinated tetrahedrane and bicyclo[1.1.1]pentane.
Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals
Authors: Balduf Ty , Caricato Marco
Published: November 2022

This work reports the derivation and implementation of the electric dipole-magnetic dipole and electric dipole- electric quadrupole polarizability tensors at density functional theory level with periodic boundary conditions (DFT-PBC). These tensors are combined to evaluate the Buckingham/Dunn tensor that describes the optical rotation (OR) in oriented chiral systems. We detail several aspects of the derivation of the equations, and present test calculations that verify the correctness of the tensors formulation and of their implementation. The results show that the full OR tensor is completely origin invariant as for molecules and that PBC calculations match molecular cluster calculations on 1D chains. A preliminary investigation on the choice of density functional, basis set, and gauge indicates a similar dependence as for molecules: the functional is the primary factor that determines the OR magnitude, followed by the basis set and to a much smaller extent the choice of gauge. However, diffuse functions may be problematic for PBC calculations even if they are necessary for the molecular case. A comparison with experimental data of OR for the tartaric acid crystal shows reasonable agreement given the level of theory employed. The development presented in this work offers the opportunity to simulate the OR of chiral crystalline materials with general purpose DFT-PBC methods, which in turn may help to understand the role of intermolecular interactions on this sensitive electronic property.
Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine's Small Molecules
Authors: Rusakov Alexander , Casetti Vincent , MacLean James , Ayoub Adam , Fredericks Rain , Adamski Jacob
Published: November 2022

We present a systematic study of electron-correlation and relativistic effects in diatomic molecular species of the heaviest halogen astatine (At) within relativistic single- and multi-reference coupled-cluster approaches and relativistic density functional theory. We establish revised reference \textit{ab initio} data for the ground states of \ce{At2}, \ce{HAt}, \ce{AtAu}, and \ce{AtO+} using a highly accurate relativistic effective core potential model and in-house basis sets developed for accurate modeling of molecules with large spin-orbit effects. Spin-dependent relativistic effects on chemical bonding in the ground state are comparable to the binding energy or even exceed it in \ce{At2}. Electron-correlation effects near the equilibrium internuclear separation are mostly dynamical and can be adequately captured using single-reference CCSD(T). However, bond elongation in \ce{At2} and, especially, \ce{AtO+} results in rapid manifestation of its multi-reference character. While useful for evaluating the spin-orbit effects on the ground-state bonding and properties, the two-component density functional theory lacks predictive power, especially in combination with popular empirically adjusted exchange-correlation functionals. This drawback supports the necessity to develop new functionals for reliable quantum-chemical models of heavy-element compounds with strong relativistic effects.
How to Enhance the Efficiency of Breslow Intermediates for SET Catalysis
Authors: Mulks Florian F. , Melaimi Mohand , Yan Xiaoyu , Baik Mu-Hyun , Bertrand Guy
Published: November 2022

Oxidative carbene organocatalysis, which proceeds via single electron transfer (SET) pathways, has been limited by the moderately reducing properties of deprotonated Breslow intermediates BI−s derived from thiazol-2-ylidene 1 and 1,2,4-triazolylidene 2. Using computational methods, we assess the redox potentials of BI−s based on ten different types of known stable carbenes and report our findings concerning the key parameters influencing the steps of the catalytic cycle. From the calculated values of the first oxidation potential of BI−s derived from carbenes 1 to 10, it appears that apart from the diamidocarbene 7, all the others are more reducing than thiazol-2-ylidene 1 and the 1,2,4-triazolylidene 2. We observed that while the reducing power of BI−s significantly decreases with increasing solvent polarity, the redox potential of the oxidant can increase at a greater rate, thus facilitating the reaction. The cation, associated with the base, also plays an important role when a non-polar solvent is used; large and weakly coordinating cations such as Cs+ are beneficial. The radical-radical coupling step is probably the most challenging step due to both electronic and steric constraints. Based on our results, we predict that mesoionic carbene 3 and abnormal NHC 4 are the most promising candidates for oxidative carbene organocatalysis.
Measurement of Tryptophan in Cell Cultures Using Fast Scan Cyclic Voltammetry at Carbon Fiber Microelectrodes with Improved Sensitivity and Selectivity
Authors: Schapira Isabella , Russo-Savage Lillian , Narla Terdha , O'Neill Maggie , Laprade Kathryn , Stafford James , Ou Yangguang
Published: November 2022

Establishing a sensitive and selective method to measure tryptophan in situ with good spatiotemporal resolution is invaluable to understanding its biological role and activity in nutrition, health, brain disorders, and the gut-brain axis. Here, we report on a sensitive and selective method to measure tryptophan over its main interfering species tyrosine. Specifically, we achieve this using fast scan cyclic voltammetry at carbon fiber microelectrodes via the application of an optimized multi-scan rate sawhorse waveform. We report over four-fold increase in sensitivity over previously reported methods and a six-fold selectivity of tryptophan quantitation over that of tyrosine. We demonstrate the utility of our method via measuring extracellular Trp in cultured PC-12 cells and PC-12 cells with overexpressed tryptophan hydroxylase 2.