Conformational Analysis of Trimethylene Sulfites. The Importance of Vicinal Unshared Electron Pairs

1971 ◽  
Vol 49 (8) ◽  
pp. 1202-1208 ◽  
Author(s):  
Gordon Wood ◽  
John M. McIntosh ◽  
Maurice H. Miskow
Keyword(s):  
Conformational Analysis ◽  
Electron Pair ◽  
Dipole Moments ◽  
General Scheme ◽  
The Other ◽  
Ultrasonic Absorption ◽  
Electron Pairs ◽  
Alkyl Derivatives ◽  
Available Information ◽  
Rule Out

Dipole moments are reported for trimethylene sulfite and 11 alkyl derivatives in a variety of solvents (C6H12, CCl4, C6H6, dioxan). The variation of dipole moment with solvent for one of the 5-t-butyltrimethylene sulfite isomers is confirmed, but this behavior is not shown by the other compounds. This latter fact is used to rule out rapid chair–chair interconversion for these compounds. Recent ultrasonic absorption experiments are reinterpreted in the context of vicinal electron pair interactions and their effect on conformational analysis of sulfites and similar six-membered compounds. The result is a general scheme which is consistent with available information and which we believe is preferable to analysis of these compounds by analogy with cyclohexane.

The gauche effect on conformation. α-Substituted sulfones and N-substituted sulfonamides

1979 ◽  
Vol 44 (11) ◽  
pp. 3378-3384 ◽  
Author(s):  
Otto Exner ◽  
Jan B. F. N. Engberts
Keyword(s):  
Lone Electron Pair ◽  
Electron Pair ◽  
Benzene Solution ◽  
Dipole Moments ◽  
Conformational Preference ◽  
Electron Pairs ◽  
Gauche Effect

The dipole moments of α-halogenosulfones IIa-f in benzene solution revealed the conformation C, those of N-methyl-N-nitrosulfonamides IIIa-c the conformation F. In either case the conformational preference is governed by the gauche rule which may be worded in a modified version that symmetrical positions of polar bonds and/or of lone electron pairs are disfavoured. A lone electron pair appears to be more significant than a polar bond.

Electron detachment from anions in aqueous solutions studied by two- and three-pulse femtosecond spectroscopy

2010 ◽  
Vol 82 (10) ◽  
pp. 1919-1926 ◽  
Author(s):  
Hristo Iglev ◽  
Martin K. Fischer ◽  
Alfred Laubereau
Keyword(s):  
Diffusion Coefficients ◽  
Strong Influence ◽  
Electron Pair ◽  
Hydrated Electron ◽  
The Other ◽  
Electron Detachment ◽  
Electron Pairs ◽  
Electron Photodetachment ◽  
Relaxation Channel ◽  
The One

The electron photodetachment of the aqueous halides and hydroxide is studied after resonant excitation in the lowest charge-transfer-to-solvent (CTTS) state. The initially excited state is followed by an intermediate assigned to a donor-electron pair that displays a competition of recombination and separation. Using pump–repump–probe (PREP) spectroscopy, the pair species is verified via a secondary excitation with separation of the pairs so that the yield of released electrons is increased. The observed recombination process on the one hand and the similar absorptions of the intermediate and the hydrated electron on the other hand suggest that the donor-electron pairs incorporate only few if not just one water molecule. The geminate dynamics measured in the various CTTS systems reveal a strong influence of the parent radical. The electron survival probability decreases significantly from 0.77 to 0.29 going from F– to OH–. The extracted dissociation rates of the halogen-electron pairs seem to be proportional to the mutual diffusion coefficients of the geminate particles, while such a relation between the recombination rate and the diffusion coefficient is not found. Results for I– show that excitation of a higher-lying CTTS state opens a new relaxation channel, which directly leads to a fully hydrated electron, while the relaxation channel discussed above is not significantly affected.

Modernism, Empiricism, and Rationalism

2016 ◽  
Vol 46 (1) ◽  
pp. 38-47
Author(s):  
Geoffrey Squires
Keyword(s):  
Twentieth Century ◽  
The Other ◽  
Modern Poetry ◽  
Philosophical Perspective ◽  
Irish Poetry ◽  
Dimensional Spectrum ◽  
Culture History ◽  
The World ◽  
The Impact ◽  
Rule Out

Modernism is usually defined historically as the composite movement at the beginning of the twentieth century which led to a radical break with what had gone before in literature and the other arts. Given the problems of the continuing use of the concept to cover subsequent writing, this essay proposes an alternative, philosophical perspective which explores the impact of rationalism (what we bring to the world) on the prevailing empiricism (what we take from the world) of modern poetry, which leads to a concern with consciousness rather than experience. This in turn involves a re-conceptualisation of the lyric or narrative I, of language itself as a phenomenon, and of other poetic themes such as nature, culture, history, and art. Against the background of the dominant empiricism of modern Irish poetry as presented in Crotty's anthology, the essay explores these ideas in terms of a small number of poets who may be considered modernist in various ways. This does not rule out modernist elements in some other poets and the initial distinction between a poetics of experience and one of consciousness is better seen as a multi-dimensional spectrum that requires further, more detailed analysis than is possible here.

scholarly journals EXPRESS: When Two Actors Perform Different Tasks: Still No Evidence for Shared Task-Sets in Joint Task Switching

2021 ◽  
pp. 174702182110315
Author(s):  
Motonori Yamaguchi ◽  
Husnain H. Shah ◽  
Bernhard Hommel
Keyword(s):  
Task Switching ◽  
The Other ◽  
Shared Task ◽  
Joint Condition ◽  
Task Instructions ◽  
Switch Costs ◽  
Joint Task ◽  
Task Sets ◽  
Rule Out

Two different variations of joint task switching led to different conclusions as to whether co-acting individuals share the same task-sets. The present study aimed at bridging this gap by replicating the version in which two actors performed two different tasks. Experiment 1 showed switch costs across two actors in a joint condition, which agreed with previous studies, but also yielded even larger switch costs in a solo condition, which contradicted the claim that actors represent an alternative task as their own when it is carried out by the co-actor but not when no one carries it out. Experiments 2 and 3 further examined switch costs in the solo condition with the aim to rule out possible influences of task instructions for and experiences with the other task that was not assigned to the actor. Before participants were instructed on the second of the two tasks, switch costs were still obtained without a co-actor when explicit task names (“COLOUR” and “SHAPE”) served as go/nogo signals (Experiment 2), but not when arbitrary symbols (“XXXX” and “​​​​”) served as go/nogo signals (Experiment 3). The results thus imply that switch costs depend on participants’ knowledge of task cues being assigned to two different tasks, but not on whether the other task is performed by a co-actor. These findings undermine the assumption that switch costs in the joint conditions reflect shared task-sets between co-actors in this procedure.

If in Doubt, Leave it Out? EU Precaution in WTO Regulatory Space

2010 ◽  
Vol 1 (1) ◽  
pp. 20-30 ◽  
Author(s):  
James Flett
Keyword(s):  
European Union ◽  
Political Authority ◽  
The Other ◽  
The Political ◽  
International Level ◽  
Eu Law ◽  
The European Union ◽  
International Organisations ◽  
Balanced Approach ◽  
Available Information

This article reviews the way in which the concept of precaution, as commonly referenced in EU law, is received in the WTO. It argues that precaution is not a principle, but one facet of a principle of making rational judgments based on available information, the other facet of which is “that risk is worth taking”. Systematically pursuing high cost measures in response to low risks is not a balanced approach, and has probably contributed to the scepticism with which the concept is viewed in the WTO. However, this article goes on to argue that, without needing to be a principle, precaution is the determining legal feature in the SPS Agreement, because, unlike in the European Union, there is no legislative harmonisation of SPS measures at international level, WTO Members being free to set their own appropriate level of protection. In fact, the concept of precaution is relevant in the context of many other WTO provisions and is in some respects quite close to the concept of subsidiarity. Notwithstanding this, the first WTO SPS cases, driven by regulatory exporters and an interventionist WTO, have excessively emphasised scientific issues, masking policy judgments that the WTO has neither the legal nor the political authority to sustain. The article concludes that the proper way forward necessitates closer political, legal and administrative links between the WTO and other relevant international organisations, and a move away from consensus in the latter.

Are mesoionic compounds aromatic?

1998 ◽  
Vol 76 (6) ◽  
pp. 869-872 ◽  
Author(s):  
Alfredo Mayall Simas ◽  
Joseph Miller ◽  
Petrônio Filgueiras de Athayade Filho
Keyword(s):  
Experimental Evidence ◽  
Key Words ◽  
Dipole Moments ◽  
The Other ◽  
Side Chain ◽  
Theoretical Studies ◽  
X Ray Diffraction ◽  
Ring Plane ◽  
X Ray ◽  
Single Bonds

We have evaluated the experimental evidence relevant to the structure and character of mesoionic compounds, accumulated for more than 100 years and including X-ray diffraction studies. We have also evaluated relevant theoretical studies. All these, including our own extensive work, lead us to conclude that mesoionic compounds are not aromatic. According to our recent definition “mesoionic compounds are planar five-membered heterocyclic betaines with at least one side chain whose α-atom is also in the ring plane and with dipole moments of the order of 5 D. Electrons are delocalized over two regions separated by what are essentially single bonds. One region, which includes the a-atom of the side chain is associated with the HOMO and negative π-charge whereas the other is associated with the LUMO and positive π-charge.” Key words: mesoionic compounds, betaines, aromaticity.

scholarly journals The Glucosamine Controversy; A Pharmacokinetic Issue

2011 ◽  
Vol 14 (2) ◽  
pp. 264 ◽  
Author(s):  
Ali Aghazadeh-Habashi ◽  
Fakhreddin Jamali
Keyword(s):  
Clinical Trial ◽  
Animal Studies ◽  
The Other ◽  
Naturally Occurring ◽  
Assessment Metrics ◽  
Disease Modifying ◽  
Clinical Trial Results ◽  
Higher Doses ◽  
Positive Results ◽  
Rule Out

Glucosamine (GlcN) is a naturally occurring aminosugar that is widely used to treat osteoarthritis despite controversial clinical trial results. Animal studies, on the other hand, unequivocally suggest anti-inflammatory and disease modifying effects for GlcN. Many explanations have been offered as to the root of the controversy. They include superiority of a crystalline sulphate salt over HCl, industry bias, insensitive assessment metrics and poor methodology. Herein, we rule out a difference in bioequivalence between GlcN salts and that of chemically equivalent doses and suggest additional factors; i.e., inconsistency in the chemical potency of some products used, under-dosing of patients as well as variable and erratic bioavailability indices for the lack of GlcN efficacy observed in some studies. Clinical trials using higher doses of pharmaceutical grade GlcN or formulations with greater bioavailability should yield positive results. This article is open to POST-PUBLICATION REVIEW. Registered readers (see “For Readers”) may comment by clicking on ABSTRACT on the issue’s contents page.

scholarly journals REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS

2020 ◽  
Vol 86 (7) ◽  
Author(s):  
Anatolii Popov ◽  
Illia Kapitanov ◽  
Anna Serdyuk ◽  
Aleksandr Sumeiko
Keyword(s):  
Organic Phosphorus ◽  
Organophosphorus Pesticides ◽  
Reaction Rates ◽  
Hydroxamic Acids ◽  
Phosphorus Compounds ◽  
Reaction Products ◽  
Electron Pairs ◽  
Alkyl Derivatives ◽  
Solvent Type ◽  
Electron Deficiency

The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc.

scholarly journals Rewiry metafory. Między ozdobą dyskursu a zwierciadłem duszy

2019 ◽  
Vol 31 ◽  
pp. 46-69
Author(s):  
Katarzyna Popek
Keyword(s):  
Donald Davidson ◽  
The Other ◽  
Gottlob Frege ◽  
Ernst Cassirer ◽  
Rhetorical Tradition ◽  
Complex Sentences ◽  
George Lakoff ◽  
Definition Of ◽  
Linguistic Phenomenon ◽  
Rule Out

The purpose of the text is to make some reconnaissance in the area of title "districts of metaphor" (or hunting grounds of metaphor) as well as reference to the unsolvable problems which are implied by a metaphorical mystery of metaphysical expressions. Thy are the order of the day in the main currents of philosophy. Starting from the rhetorical tradition of metaphor (the Aristotelian attempts of definition of metaphor as such) and of terms additional related with it (Max Black), I gradually illustrate what involves its post-rhetorical tradition. I show that philosophical symbolism derives from Aristotle’s hermeneutics, which becomes a gateway for understanding the mystery of metaphor. Like browsing in themselves mirrors, it grows also from simple phrases in complex sentences. In semantic sense, while the symbol has many meanings, the metaphor has a double meaning. It is not however limited by this matter, because in some sense, it has broader content than a symbol, as it introduces into language meanings that in the symbol are only internal (Paul Ricoeur). We also encounter reflective metaphors in our everyday speech and in the attempts of associative penetration into other people's expression. Conceptual decoding of metaphors is common for users of language (George Lakoff, Mark Johnson). On the other hand, there are specific districts of metaphorical expressions, which are reserved for poetic metaphors (Donald Davidson). Noteworthy are also the very unobvious contexts of metaphor in which the authors do not talk about this linguistic phenomenon directly (eg. Gottlob Frege, Ernst Cassirer). Declarative answer to the question whether the metaphor is a simply ornament of discourse or rather a mirror of the soul, is not possible too. Perhaps the metaphor as such includes the both variants. One must consider that being an ornament of speech or writing does not rule out it is also something more than just decoration. It wonders, bothers, disquiet, returning us into our souls. It is also like the unifying soul of all people – in cognitive sense.

scholarly journals Sharia Life Insurance Business and Risk Management Based on Sharia Principles: Regulatory Perspective

2021 ◽  
Vol 21 (2) ◽  
pp. 395-414
Author(s):  
Parmujianto Parmujianto
Keyword(s):  
Risk Management ◽  
Life Insurance ◽  
Qualitative Approach ◽  
The Other ◽  
Theoretical Contribution ◽  
Depth Data ◽  
Regulatory Perspective ◽  
Insurance Business ◽  
Business Entities ◽  
Rule Out

Abstract: Sharia life insurance is an agreement between two parties. One is obliged to pay a contribution or premium, and the other must ensure a full guarantee of the insurers. It should undertake the protection of a contingent or uncertain loss based on the contract. This research used a descriptive qualitative approach. It seeks to explore and understand the central phenomenon to obtain in-depth data to reveal the facts on the research object. The theoretical contribution in this study can contribute to the insights about the insurance partnership of ASYKI, Inc. to increase the number of insurance participants. It is expected that people do not have doubts about sharia life insurance in a formal juridical manner related to insurance. The result of the research showed that Asuransi Shariah Keluarga Indonesia ASYKI, Inc Pasuruan Unit's performance is generally good. According to Law No.40 of 2014, its risk management is sharia-oriented. However, it does not rule out individuals who register individually. Still, ASYKI, Inc. Pasuruan Unit provides some solutions. They should register with the ASYKI partners. It opens an opportunity for the polis applicants to easily recognize and apply sharia life insurance without going through business entities or companies that act as intermediaries.الملخص: التأمين على الحياة في الشريعة هو تأمين أو اتفاق بين طرفين يلتزم فيه أحد الطرفين بدفع  تراكات أو أقساط والآخر ملزم بتقديم ضمانات كاملة لدافعي الاشتراكات / الاشتراكات / الأقساط إذا حدث شيء ما الطرف الأول أو ممتلكاته وفقًا للاتفاق المبرم. النهج المستخدم في هذه الدراسة هو نهج وصفي نوعي. يسعى هذا النهج إلى استكشاف وفهم الظاهرة المركزية من أجل الحصول على بيانات متعمقة لكشف الحقائق التي حدثت في موضوع البحث. يمكن أن تساهم المساهمات النظرية في هذه الدراسة في المعرفة حول شراكة التأمين لـ PT. ASYKI في زيادة عدد المشاركين في التأمين. من الناحية العملية حتى لا يساور الناس شك حول التأمين الشرعي على الحياة ، سواء من الناحية القانونية أو الرسمية المتعلقة بالتأمين .وقد أظهرت نتائج هذه الدراسة أن PT. تعتبر وحدة ASYKI Pasuruan  للتأمين الشرعي للأسرة الإندونيسية بشكل عام جيدة ووفقًا للقانون رقم 40 لعام 2014 في إدارة إدارة المخاطر على أساس مبادئ الشريعة الإسلامية ، على الرغم من أنه من الممكن للأفراد التسجيل بشكل فردي ، وهو الحل الذي تقدمه PT. يجب أن تسجل وحدة  ASYKI Pasuruan بوالص التأمين الموجهة بشكل فردي إلى أحد الشركاء الذين يعملون مع PT. سيفتح ASYKI وفي المستقبل فرصًا لمسجلي السياسة الفردية بحيث يكون الجمهور أكثر حرية في التعرف على التأمين على الحياة وتطبيقه وفقًا للشريعة بسهولة دون الحاجة إلى المرور عبر كيان تجاري أو شركة تعمل كوسيط. Abstrak: Asuransi jiwa syari’ah merupakan pertanggungan atau perjanjian antara dua belah pihak yangmana pihak satu berkewajiban membayar kontribusi atau premi dan yang lainnya memiliki kewajiban memberikan jaminan sepenuhnya kepada pembayar iuran/kontribusi/premi apabila terjadi sesuatu yang menimpa pihak pertama atau barang miliknya sesuai dengan perjanjian yang sudah dibuat. Pendekatan yang digunakan dalam penelitian ini adalah pendekatan kualitatif deskriptif.  Pendekatan  ini berusaha mengekplorasi dan memahami gejala sentral agar mendapatkan data yang mendalam guna mengungkapkan fakta yang terjadi pada objek penelitian. Kontribusi teoritis  dalam penelitian ini dapat memberikan sumbangsih ilmu pengetahuan tentang kemitraan asuransi  PT. ASYKI dalam menambah jumlah peserta asuransi. Adapun secara praktis agar masyarakat tidak memiliki keraguan mengenai asuransi jiwa shariah, baik secara yuridis formal yang berhubungan dengan perasuransian. Hasil dari penelitian ini bahwa PT. Asuransi Shariah Keluarga Indonesia ASYKI Unit Pasuruan secara umum dan keseluruan sudah baik  dan sesuai dengan UU No.40 Tahun 2014 dalam pengelolaan manajemen resiko sudah berdasarkan prinsip shariah, meskipun tidak menutup kemungkinan ada individu yang mendaftarkan diri secara perorangan, namun solusi yang ditawarkan dari pihak PT. ASYKI Unit Pasuruan hendaknya pendaftar poli asuransi secara individu di arahkan pada salah satu mitra yang bekerja sama dengan PT. ASYKI dan ke depannya akan membuka peluang bagi pendaftar polis secara perorangan sehingga masyarakat lebih leluasa untuk mengenal dan menerapkan asuransi jiwa shariah dengan mudah tanpa harus melalui badan usaha atau perusahaan yang menjadi perantara.

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