48 research outputs found
Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes
No full textFrustrated Lewis pairs (FLPs) are powerful, typically nonmetal, Lewis acid/base combinations that can split dihydrogen (H2) heterolytically, due to their inability to form conventional Lewis adducts (usually as a result of steric repulsion). The H2 thus activated can be transferred to various substrates in a catalytic fashion. The scope of substrates catalytically hydrogenated with FLPs is rapidly expanding, approaching that of transition-metal-catalyzed hydrogenations. The discovery of FLPs is, perhaps, one of the most remarkable recent findings in the field of main group organometallic compounds. The literature review part provides a brief critical overview of heterolytic H2 splitting with FLPs, including the thermodynamic, mechanistic, and catalytic aspects of this process. Particular emphasis is placed on the Lewis acidity of various boranes, since this factor is critical for the ability of FLPs to split H2 and provides a basis for introducing fluoroaryl-free boranes into the FLP area. The experimental section of the thesis is devoted to the development of FLP catalysts, based on an ansa-aminoborane core for hydrogenation of various substrates. Within the study, various parts of the ansa-aminoborane molecule were modified: a amine group, resulting in highly active ansa-aminoboranes for hydrogenation of imines and other nitrogen-containing compounds, also featuring other unique properties; a mutual B/N geometry (changing the nature of the link), resulting in an ansa-catalyst for hydrogenation of unactivated alkynes; and a borane part, revealing that lightweight and inexpensive ansa-aminochloroboranes show reactivity to H2 similar to that of C6F5 boranes, including catalytic abilities. A book chapter covering recent progress in frustrated borane/amine Lewis interaction, involving ansa-systems was included in the thesis.Molekyylien pelkistäminen vetykaasulla on orgaanisen kemian tärkeimpiä reaktioita. Useimmiten reaktio ei etene itsestään, vaan siihen tarvitaan katalyytti. Vedytyskatalyytit sisältävät tavallisesti kalliita jalometalleja kuten palladiumia, platinaa, rodiumia tai ruteniumia. Vety siirtyy substraatille labiilin metalli-H2 välituotteen kautta. Hiljattain on osoitettu, että tietynlaiset metallittomat yhdisteet, joita kutsutaan turhautuneiksi Lewis-pareiksi, voivat reagoida vedyn kanssa ja jopa toimia katalyytteina monissa pelkistysreaktiossa. Tässä työssä käsitellään yhdisteitä, joiden aktiiviset keskukset, boori ja typpi, on tuotu samassa molekyylissä toistensa lähelle (ansa-aminoboraanit). Nämä ovat tehokkaita vedytyskatalyytteja monille erilaisille substraateille. Työssä syntetisoitiin myös moolimassaltaan kevyitä aminoboraaneja, jotka osoittavat mahdollisuuden käyttää tällaisia yhdisteitä vedyn varastointia varten.ei saavutettav
THE MAXIM “LAW DOES NOT ARISE FROM THE VIOLATION OF LAW” AND THE MODIFICATION OF PEREMPTORY NORMS
No full textMaxim “ex injuria jus non oritur” is not only a general legal, but also an international legal
principle, which states that law doesn’t arise from the violation of law. However, peremptory
norms of international law (jus cogens) are not something frozen. They develop, like
international law in general, so the latter expressly provides for the possibility of their
modification by subsequent norms of the same nature. This inevitably means that, in the
period of changing such norms, the behavior of some states will contradict the previous
peremptory norm until the emergence of a new peremptory norm is recognized by the
international community of states. Does the change of imperative norms result in an exception
to the above-mentioned maxim? And how do you know whether the actions of the
state or group of states have created a new peremptory norm of international law, or they
are merely a violation of the already existing peremptory norm? Can moral considerations
justify the state’s withdrawal from the maxim of “ex injuria jus non oritur” in the name of
creating a new peremptory norm of international law? Or is such a deviation justified by
the conformity of the state’s actions to any other norms? Having examined these issues,
the author comes to the conclusion that, unlike the positive law, natural law does not know
exceptions to the maxim. The author proves that the ground for the emergence of new
peremptory norms of international law creates changes in natural law
THE EUROPEAN COURT ON HUMAN RIGHTS: THE PROBLEM OF UNENFORCEABLE JUDGMENTS
No full textINTRODUCTION. The paper demonstrates that the problem of implementing judgments of the European Court of Human Rights does exist if such a judgment is not in line with the Constitution of the Russian Federation. This problem is caused in legal dimension by the two different factors. On the one hand the Constitution of the Russian Federation “shall be the supreme law and shall be in force throughout the territory of the Russian Federation. No laws or other legislative acts … shall contravene the Constitution of the Russian Federation” (Article 15 Part 1). On the other hand, a State may not invoke its internal (national) law as justification for its failure to perform a treaty (Article 27 of the Vienna Convention on the Law of Treaties, 1969).MATERIALS AND METHODS. Research materials include judgments of the European Court of Human Rights and Orders of the Constitutional Court of the Russian Federation and also the teachings of the most qualified scholars in International Law which are relevant to the title of this paper. General and specific scientific methods are used by the author. In the context of applicable general international law the paper considers both judgments o the European Court of Human Rights and orders of the Constitutional Court of the Russian Federation paying specific attention to the reasons of different legal positions adopted by these Courts.RESEARCH RESULTS. The widening of the competence of the Сonstitutional Court of Russia in December 2014 arouses apprehension. The Court pointed out that two judgments of the European Court on Human Rights were unenforceable: (1) on the judgment on the application of Anchugov and Gladkov and (2) on the judgment concerning the application of UKOS. In the first case the European Court on Human Rights admitted that Russia was responsible for moral damage and the recognition of it was enough for compensation. In the second case the European Court on Human Rights admitted that Russia violated Protocol No.1 to the Convention on Human Rights. In connection with it Russia must compensate the pecuniary damage. It is confirmed by the Committee of Ministers (the Council of Europe).DISCUSSION AND CONCLUSIONS. The Constitutional Court of the Russian Federation indeed has (as its professional function) an obligation to legally protect the national interests of Russia if they are questioned by a judgment of a foreign court which does not correspond to International Law. But in cases considered in this paper the Constitutional Court of Russia while addressing the judgments of the European Court of Human Rights (which are in contradiction with the International Law) made itself a legal mistake from the point of International Law. According to Article 26 of the Vienna Convention on the Law of Treaties, 1969, every treaty in force is binding upon the parties to it and must be performed by them in good faith”. Even in the case when the national law provides for a different approach (article 27 of the same Convention). The Constitution of any State is a part of its national law. So the 1969 Convention’s rules of Articles 26 and 27 are applicable also to Constitutions. While stating that the Constitution has a higher legal value then International Treaty of the Russian Federation, the Constitutional Court thus undermines the national interests of Russia in maintaining legal order and the Rule of Law in international relations
Characteristics and Analysis of Speech Development Disorders in Early Children
No full textСтаття присвячена характеристиці та аналізу порушень мовленнєвого розвитку у дітей раннього віку. У кожній країні є діти з важкими порушеннями мовлення, якi потребують особливих умов навчання та виховання. На сьогоднi дуже актуальними є питання надання кваліфікованої корекційно-розвиткової допомоги таким дiтям. Розлади мовленнєвого розвитку знаходяться на вивченні у багатьох спеціальностей. Мовленнєва функція є основною та ключовою для розвитку мислення та інтелекту дитини, тому порушення формування мовлення неминуче тягне за собою відставання у розвитку інтелекту, мислення, порушення спілкування та соціалізації, виникнення поведінкових порушень. Порушення мовленнєвого розвитку можуть бути спричинені різноманітними захворюваннями, які зустрічаються в загальній педіатричній практиці. Одними із таких причин можуть бути порушення артикуляційного апарату, хронічні отити, що призводять до порушення слуху, епілепсія та епілептичні енцефалопатії, ДЦП та багато інших захворювань. У статті висвітлено проблематику, що в даний час логопеди – практики відчувають недостатність розроблених ефективних методик щодо подолання мовленнєвих порушень у дітей раннього віку. У зв'язку з цим необхідно вивчати розлади експресивного та імпресивного мовлення, які охоплюють всі сфери особистості дитини. У спеціальній педагогіці йде активний пошук найбільш оптимальних форм організації освітнього та корекційного-розвиткового середовища для цієї категорії дітей. У огляді наукової літератури проведено аналіз даних, що стосуються розладів мовленнєвого розвитку дітей раннього віку. Автор аналізує особливості міжнародних та вітчизняних класифікацій порушень розвитку мовлення в ранньому віці, найбільш часто зустрічаються клінічні варіанти цієї патології. Паралельно розглядається етіологія затримок розвитку мовлення в залежності від їх захворювання.The article is devoted to the characteristics and analysis of disorders of speech development in young children. Every country has children with severe speech disorders who require special conditions for education and upbringing. Today, the issue of providing qualified correctional and developmental assistance to such children is very relevant. Disorders of speech development are studied in many specialties. The speech function is the main and key for the development of a child's thinking and intelligence, therefore, a violation of the formation of speech inevitably entails a delay in the development of intelligence, thinking, communication and socialization disorders, and the emergence of behavioral disorders. Disturbances in speech development can be caused by a variety of diseases that occur in general pediatric practice. One of these reasons can be disorders of the articulation apparatus, chronic otitis media leading to hearing impairment, epilepsy and epileptic encephalopathies, cerebral palsy and many other diseases. The article highlights the problem that currently speech therapists - practitioners feel the insufficiency of developed effective methods for overcoming speech disorders in young children. In this regard, it is necessary to study disorders of expressive and impressive speech, which cover all spheres of the child's personality. In special pedagogy, there is an active search for the most optimal forms of organizing an educational and corrective-developmental environment for this category of children. In the review of scientific literature, an analysis of data related to disorders of speech development of young children was carried out. The author analyzes the features of international and domestic classifications of speech disorders at an early age, the most common clinical variants of this pathology. At the same time, the etiology of speech development delays depending on their disease is considered
Pretraining graph transformers with atom-in-a-molecule quantum properties for improved ADMET modeling
No full textAbstract We evaluate the impact of pretraining Graph Transformer architectures on atom-level quantum-mechanical features for the modeling of absorption, distribution, metabolism, excretion, and toxicity (ADMET) properties of drug-like compounds. We compare this pretraining strategy with two others: one based on molecular quantum properties (specifically the HOMO-LUMO gap) and one using a self-supervised atom masking technique. After fine-tuning on Therapeutic Data Commons ADMET datasets, we evaluate the performance improvement in the different models observing that models pretrained with atomic quantum mechanical properties produce in general better results. We then analyze the latent representations and observe that the supervised strategies preserve the pretraining information after fine-tuning and that different pretrainings produce different trends in latent expressivity across layers. Furthermore, we find that models pretrained on atomic quantum mechanical properties capture more low-frequency Laplacian eigenmodes of the input graph via the attention weights and produce better representations of atomic environments within the molecule. Application of the analysis to a much larger non-public dataset for microsomal clearance illustrates generalizability of the studied indicators. In this case the performances of the models are in accordance with the representation analysis and highlight, especially for the case of masking pretraining and atom-level quantum property pretraining, how model types with similar performance on public benchmarks can have different performances on large scale pharmaceutical data. Scientific contribution We systematically compared three different data type/methodologies for pretraining molecular Graphormer with the purpose of modeling ADMET properties as downstream tasks. The learned representations from differently pretrained models were analyzed in addition to comparison of downstream task performances that have been typically reported in similar works. Such examination methodologies, including a newly introduced analysis of Graphormer’s Attention Rollout Matrix, can guide pretraining strategy selection, as corroborated by a performance evaluation on a larger internal dataset
Experimental synthetic approach to segment assessment of aggregate credit risk
No full textMultifaceted, multifactor and multicomponent nature of credit risk makes it possible to consider it as an integral hypothetical unit which consists of the autonomous diverse segments specifying risky situations. As the given article is focused on the mechanism of loan fund circulation within foreign currency loan the author considers the combination of credit, interest rate, foreign exchange and inflation risks within the aggregate (total, combined) credit risk. Foreign exchange and inflation risks generate special interest in relation to evaluation procedures as there can be statutory regulation of interest rate risk and well-functioning mechanism of debt capacity analysis as the main factor of credit risk. As commercial loans and bank credits taken by Russian companies are wide spread the authors of the article suggest an innovative procedure of aggregate credit risk assessment considering agricultural companies, as well as companies belonging to chemical and machine-building industries as «pure borrowers» (debtors). The research has a set sequence of procedures. During the first stage the authors structured a risky situation in the lending process, determined specific constituents and performed their further strategic agreement. The second stage implies the analysis of the possibilities and specific characteristics of the preliminary segment assessment of the risk level. The third stage involves the development of experimental synthetic approach to the segment assessment of the aggregate credit risk in case of foreign exchange rate and interest rate volatility when there are inflation expectations. The procedure considers the following scenarios: 1) isolated assessment of inflation risk; 2) isolated assessment of exchange rate risk; 3) complex assessment of inflation and exchange rate risks
Following up the Discussion on the stricto sensu ‘Principles’ in Modern International Law, and Beyond the Same ….
No full textINTRODUCTION. The situation in domestic legal science of Russia in the field of research of the subject of principles in international law may be ascertained in general terms as a fairly static picture that inspires a serene belief in the immutability of the existing position and further stable sustainability thereof. Such state of things consists in the illusion of the non-availability of difficulties or problems – a person starts from the point of a binary opposition in the values of principles / norms, as well as the unchangeable existence of the dichotomy of basic and sectoral principles. At the same time, let’s take note, that sectoral principles are alternatively and in most cases equivalently treated as special ones [Chernichenko 2014:101-102]. The implications of the said assumption are ideas relevant to sectoral principles as based on the presumption of their similarity in essence and function, based only on the name and place in the regulatory system (branch of law). Undoubtedly, the general tendencies for the sectoral principles of the International Law (IL) are those, which, firstly, appear like basic ones, objectively, and, secondly, the lists and scope thereof depend from specific relations immune to particular branches of law. At the same time, with due account to the submissions afore-referred, the affected area is in many aspects significantly various, not simple and can give rise to many differing views, discussions, objections, rejection or support, etc., because it is conditioned by the real fact of availability in international law of a greater variety of substances/ other phenomena in the matter of principles. Due to the above, a more meticulous view of the principles in international law shall be required: on the one hand, revealing the rationale for the fact that they are not a chaotic phenomenon within the system of international law, and, on the other hand, providing a substantive analysis of them, taking into account the differentiation and identification of objects that claim to be placed under the head of principles, construing the typology thereof, etc. Such an approach is not only assumed as logical, but prima facie due by time and, therefore, fully justified.MATERIALS AND METHODS. The article is based on the provisions of international treaties, materials of codification of international law norms by the UN International Law Commission, judicial decisions, acts of law enforcement of the International Court of Justice or other international courts, and documents embodying the positive international law, as well as the teachings of the most highly qualified publicists in the field of theory and practice of international law. The research operates with various general and particular methods of analysis: dialectical materialism, structural and system analysis, formal logic, deduction and induction, comparative law, historical and retrospective approach, formal legal analysis, legal modeling, “techniques of evidence” (legal reasoning), as well as various methods of legal interpretation, etc., adopted in domestic and expatriate jurisprudence.RESARCH RESULTS. The purpose of this publication is to endeavor certain clarification of theoretical data related to such a fundamental category as “the principle of international law”, which is deemed to canbe achieved through proper identification of various constructions that operate with the element “principles” or similar terms, by way of systematization and delineation thereof from other phenomena available in the framework of international legal reality. Therefore, it is not occasional that the title of the article operates with such a formula to designate the discourse: “…. on the stricto sensu ‘principles’ in modern international law and beyond...”. To ensure the better links of the scope and objectives of the research in terms of highlighting the system of principles and smooth functioning both of international law itself and the entirety of its principles and norms, as well as to clarify and streamline the basic terminology and conceptual basis of international legal science in the matter of principles, the typology of concepts that form the legal backgrounds for contemporary regulation of interstate relationships has been commissioned herein, since there is heterogeneity of various heads of items that claim to be the principles of international law, even with no normative nature in some of them, etc. The same appears to be quite obvious facts. In witness of the same, there are, on the one hand, diversification of the normative principles expressed in modern international law, which determines the identifying features for each of existing heads of principles, and as an outcome of the latter, the need to build up the respective system, on the other hand. However, the grounds for “stratification”, i.e. the distribution of the principles per separate groups (for example, the subdivision into basic and sectoral principles or differentiation between the system-wide and special principles), are far from being exhaustively revealed as yet, and need in better targeted efforts of scholars. Due to the above, the author held differentiating sectoral and special principles inter se, having substantiated the segregation of the specific head of principles within the latter group – “principles of autonomous (self-contained) legal regimes”.DISCUSSION AND CONCLUSIONS. It seems that there is a serious substantive distinction between the formula “principles of modern international law” and “principles in modern international law”. The discourse outlined as “principles in international law”, having a broader sense and destination, in the absence of an unambiguous understanding of the term ‘the principle’, is more diligent to reflect the state of things in the field of principles in so far the legal science / international law science is concerned regarding the essence, features, and functional qualities of any particular type of objects, sometimes referred to as ‘principles’. In case, if it comes to “principles of international law”, they are to be identified primarily as the fundamental, guiding, hierarchically high norms within the system of international law, bearing the burden of the most important components of this system, and are classified according to generic and specific characteristics, which depend on their salient features. The formula “principles in international law” assumes a view of of the subject that has a broader and less structured range of options for qualifications
Nuclear Modification Factors for Hadrons At Forward and Backward Rapidities in Deuteron-Gold Collisions at = 200 GeV
No full text330 authors, 6 pages text, 4 figures, REVTeX4. To be submitted to Physical Review Letters. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.html - EIWe report on charged hadron production in deuteron-gold reactions at = 200 GeV. Our measurements in the deuteron-direction cover 1.4 < < < <_T$ = 0.5-4.0 GeV/c. We compare the relative yields for different deuteron-gold collision centrality classes. We observe a suppression relative to binary collision scaling at forward rapidity, sensitive to low momentum fraction (x) partons in the gold nucleus, and an enhancement at backward rapidity, sensitive to high momentum fraction partons in the gold nucleus
J/ Production and Nuclear Effects for and Collisions at = 200 GeV
No full text331 authors, 6 pages text, 4 figures. Submitted to PRL. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.html - EIJ/psi production in d+Au and p+p collisions at sqrt(s_NN) = 200 GeV has been measured by the PHENIX experiment at rapidities -2.2 < y < +2.4. The cross sections and nuclear dependence of J/\psi production versus rapidity, transverse momentum, and centrality are obtained and compared to lower energy p+A results and to theoretical models. The observed nuclear dependence in d+Au collisions is found to be modest, suggesting that the absorption in the final state is weak and the shadowing of the gluon distributions is small and consistent with DGLAP-based parameterizations that fit deep-inelastic scattering and Drell-Yan data at lower energies
Jet Structure of Baryon Excess in Au+Au Collisions at sqrt(S_NN) = 200 GeV
No full text396 authors, 6 pages text, 4 figures, RevTeX 4. To be submitted to PRL. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.html - EITwo particle correlations between identified meson and baryon trigger particles with 2.5 < p_T < 4.0 GeV/c and lower p_T charged hadrons have been measured at midrapidity by the PHENIX experiment at RHIC in p+p, d+Au and Au+Au collisions at sqrt(s_NN) = 200 GeV. The probability of finding a hadron near in azimuthal angle to the trigger particle is almost identical for leading mesons and baryons for non-central Au+Au. The yield for both trigger baryons and mesons is significantly higher in Au+Au than in p+p and d+Au, except for trigger baryons in central collisions. The baryon excess is likely to arise predominantly from hard scattering processes
