Lie detector

Novel, semicrystalline polyamides and copolyamides were synthesized from a new carbohydrate-based diamine, namely isoidide-2,5-dimethyleneamine (IIDMA). In combination with 1,6-hexamethylene diamine (1,6-HDA) as well as the biobased sebacic acid (SA) or brassylic acid (BrA), the desired copolyamides were obtained via melt polymerization of the nylon salts followed by a solid-state polycondensation (SSPC) process. Depending on the chemical compositions, the number average molecular weights (Mn) of the polyamides were in the range of 4000–49000 g/mol. With increasing IIDMA content in the synthesized copolyamides, their corresponding glass transition temperatures (Tg) increased from 50 °C to approximately 60–67 °C while the melting temperatures (Tm) decreased from 220 to 160 °C. The chemical structures of the polyamides were analyzed by NMR and FT-IR spectroscopy. Both differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analyses revealed the semicrystalline character of these novel copolyamides. Variable-temperature (VT) 13C{1H} cross-polarization/magic-angle spinning (CP/MAS) NMR and FT-IR techniques were employed to study the crystal structures as well as the distribution of IIDMA moieties over the crystalline and amorphous phases of the copolyamides. The performed ab initio calculations reveal that the stability of the IIDMA moieties is due to a pronounced boat conformation of the bicyclic rings. The incorporation of methylene segments in between the isohexide group and the amide groups enables the hydrogen bonds formation and organization of the polymer chain fragments. Given the sufficiently high Tm values (200 °C) of the copolyamides containing less than 50% of IIDMA, these biobased semicrystalline copolyamides can be useful for engineering plastic applications

Donor-acceptor stacking arrangements in bulk and thin-film high-mobility conjugated polymers characterized using molecular modelling and MAS and surface-enhanced solid-state NMR spectroscopy

Conjugated polymers show promising properties as cheap, sustainable and solution-processable semiconductors. A key challenge in the development of these materials is to determine the polymer chain structure, conformation and packing in both the bulk polymer and in thin films typically used in devices. However, many characterisation techniques are unable to provide atomic-level structural information owing to the presence of disorder. Here, we use molecular modelling, magic-angle spinning (MAS) and dynamic nuclear polarisation surface-enhanced NMR spectroscopy (DNP SENS) to characterise the polymer backbone group conformations and packing arrangement in the high-mobility donor-acceptor copolymer diketopyrrolo-pyrrole-dithienylthieno[3,2-b] thiophene (DPP-DTT). Using conventional H-1 and C-13 solid-state MAS NMR coupled with density functional theory calculations and molecular dynamics simulations, we find that the bulk polymer adopts a highly planar backbone conformation with a laterally-shifted donor-on-acceptor stacking arrangement. DNP SENS enables acquisition of C-13 NMR data for polymer films, where sensitivity is limiting owing to small sample volumes. The DNP signal enhancement enables a two-dimensional H-1-C-13 HETCOR spectrum to be recorded for a drop-cast polymer film, and a C-13 CPMAS NMR spectrum to be recorded for a spin-coated thin-film with a thickness of only 400 nm. The results show that the same planar backbone structure and intermolecular stacking arrangement is preserved in the films following solution processing and annealing, thereby rationalizing the favourable device properties of DPP-DTT, and providing a protocol for the study of other thin film materials

Ab-initio random structure searching of organic molecular solids : assessment and validation against experimental data

This paper explores the capability of using the DFT-D ab-initio random structure searching (AIRSS) method to generate crystal structures of organic molecular materials, focusing on a system (m-aminobenzoic acid; m-ABA) that is known from experimental studies to exhibit abundant polymorphism. Within the structural constraints selected for the AIRSS calculations (specifically, centrosymmetric structures with Z = 4 for zwitterionic m-ABA molecules), the method is shown to successfully generate the two known polymorphs of m-ABA (form III and form IV) that have these structural features. We highlight various issues that are encountered in comparing crystal structures generated by AIRSS to experimental powder X-ray diffraction (XRD) data and solid-state magic-angle spinning (MAS) NMR data, demonstrating successful fitting for some of the lowest energy structures from the AIRSS calculations against experimental low-temperature powder XRD data for known polymorphs of m-ABA, and showing that comparison of computed and experimental solid-state NMR parameters allows different hydrogen-bonding motifs to be discriminated

Unraveling unprecedented charge carrier mobility through structure property relationship of four isomers of didodecyl[1]benzothieno[3,2-b][1]benzothiophene

Since the dawn of organic electronics in the 1970’s, academic and industrial research efforts have led to dramatic improvements of the solubility, stability, and electronic properties of organic semiconductors (OSCs).[1, 2] The common benchmark to characterize the electrical performances of OSCs is their charge carrier mobility μ (cm2 V–1 s–1), defined as the drift velocity of the charge carrier (cm s–1) per unit of applied electric field (V cm–1). Reaching high mobilities in OSCs is highly desirable as it allows faster operation of transistors and energy savings by reduced calculation times.[2, 3] However, OSCs performances (conventional values usually range from 1 to 10 cm2 V–1 s–1, with highest values obtained with single-crystal devices mostly exempt of structural defects) are still not comparable to that of state-of-the-art inorganic semiconductors (e.g. metal oxides with µ = 20-50 cm2 V–1 s–1 and polycrystalline silicon with µ > 100 cm2 V–1 s–1) thereby hampering important potential technological applications such as flexible organic light-emitting diode (OLED) displays and wearable electronics.[3, 4

Impact of bazedoxifene on endothelial health markers

Atherosclerosis and its most significant clinical repercussion, cardiovascular disease (CVD), is the leading cause of morbidity and mortality in postmenopausal women, with a substantial global public health impact as a consequence. Vascular endothelial dysfunction, which is potentiated by decreasing estrogen levels in the menopausal transition period, is an early hallmark of developing CVD. The action of estrogens has been widely investigated in many critical areas of atherogenesis, due to the presence of estrogen receptors in the vascular system. Estrogens can have both positive and negative effects on the vascular wall depending on the stage of atherosclerosis disease. The estrogen response is mediated by different mechanisms, involving either genomic pathways requiring ligand-activated transcription with posterior modulation of protein synthesis, or non-genomic pathways, mainly affecting enzyme activity and rapid signaling cascades. The vigorous debate surrounding the risk/benefit profile of estrogen in the development and timing of CVD in postmenopausal women is still ongoing. Evidence that the progestin component of hormone therapy increases breast cancer risk or even attenuates the potential beneficial effects of estrogens has been paralleled by a decline in the use of hormone therapy in postmenopausal women in recent years. This data, along with problems associated with long-term use of bisphosphonates, has shifted the focus of recent research to other molecules capable of activating estrogen receptors, leading to transcriptional activity in some tissues but not in others. Selective estrogen receptor modulators (SERMs) and more recently, tissue selective estrogen complex (TSEC) have been developed as alternatives to hormonal replacement therapy (HRT).Previous experimental studies have shown the capacity of estrogens and second-generation SERM raloxifene to promote endothelial cell regrowth and improve cell survival rate in the early stages of atherosclerosis disease. Clinical trials involving bazedoxifene or conjugated estrogens plus bazedoxifene have shown cardiovascular safety in healthy postmenopausal women. However, one research group working with an atherosclerotic animal model in monkeys demonstrated that therapeutic application of bazedoxifene had no effect on atherosclerosis. What is more, bazedoxifene completely impeded the antiatherosclerotic effects of estrogen treatment in the mentioned study. To date no report has been published of bazedoxifene’s effect on vascular cell proliferation and the mechanisms involved using an in vitro model.Previous experimental studies have shown the capacity of estrogens and second-generation SERM raloxifene to promote endothelial cell regrowth and improve cell survival rate in the early stages of atherosclerosis disease. Clinical trials involving bazedoxifene or conjugated estrogens plus bazedoxifene have shown cardiovascular safety in healthy postmenopausal women. However, one research group working with an atherosclerotic animal model in monkeys demonstrated that therapeutic application of bazedoxifene had no effect on atherosclerosis. What is more, bazedoxifene completely impeded the antiatherosclerotic effects of estrogen treatment in the mentioned study. To date no report has been published of bazedoxifene’s effect on vascular cell proliferation and the mechanisms involved using an in vitro model

ЛЕКСИКО-ГРАМАТИЧНІ МОДЕЛІ ЕПІТЕТНИХ КОНСТРУКЦІЙ НАДІЙКИ ГЕРБІШ

The works of Nadiyka Gerbish, a young Ukrainian writer, have already gained recognition, but have little been studied. The article reveals the specifics of this author’s epithet constructions, in particular their lexical and grammatical models in the artistic discourse of short stories in the collection “Warm stories for coffee”. The article is based on a broad view of epithets considered not only as artistic definitions-adjectives that serve to describe objects (O. Veselovskyi, V. Zhyrmunskyi, V. Moskvin, etc.), but also as circumstances that “figuratively depict the action or the phenomenon or express an emotional attitude to them” (L. Matsko, and I. Arnold, L. Bulakhovskyi, O. Ponomariv, O. Selivanova, etc.).It is noted that in the writer’s artistic discourse the epithet-adjective is not the only model of expression, as the short stories of the collection contain epithets denoted by adverbs, nouns, noun-prepositional constructions, adjective and participial clauses. The study pay special attention to the epithets of the substantive nature known as occasional as they perform the function of attribute expressed by noun, as well as to constructions represented by nouns in genitive or instrumental case that function as uncoordinated attributes.The author often uses cross-cutting epithets (repeated many times in the same context), chains of epithet constructions (when one object is marked by two, three or more epithets that reinforce each other). It is stated that the writer applies permanent and free, common and the author’s epithets. The quantitative and qualitative characteristics of the writer’s epithet constructions allow to state that the epithet is one of the dominants of Nadiyka Gerbish’s idiostyle.Творчість Надійки Гербіш, молодої української письменниці, уже здобула визнання, проте ще мало досліджена. У статті розкрито специфіку її епітетних конструкцій, зокрема їх лексико-граматичні моделі у художньому дискурсі новел збірки «Теплі історії до кави». За основу взято широкий погляд на епітети – не лише як художні означення-прикметники, що слугують художньому опису обʼєктів (О. Веселовський, В. Жирмунський, В. Москвін та ін.), а й як обставини, які образно змальовують особу, предмет, дію чи явище або виражають емоційне ставлення до них (Л. Мацько, І. Арнольд, Л. Булаховський, О. Пономарів, О. Селіванова та ін.).Зазначено, що в художньому дискурсі письменниці епітет-прикметник – не єдина модель вираження, оскільки у новелах збірки «Теплі історії до кави» широко представлені епітети, виражені прислівниками, іменниками, іменниково-прийменниковими конструкціями, прикметниковими та дієприкметниковими зворотами. Особливо заслуговують на увагу епітети субстантивної природи – оказіональні, що виконують функцію прикладки, а також конструкції, виражені іменниками, що мають форму родового чи орудного відмінка і виконують роль неузгоджених означень. Авторка часто послуговується наскрізними епітетами (що неодноразово повторюються в одному контексті), ланцюжками епітетних конструкцій (коли один обʼєкт позначено двома, трьома і більше епітетами, які підсилюють один одного). Вказано, що письменниця послуговується й загальномовними епітетами, й індивідуально-авторськими; як постійними, так і вільними. Кількісна і якісна характеристика епітетних конструкцій письменниці дозволяє стверджувати, що епітет – одна із домінант мовостилю Надійки Гербіш

Features of Corporate Liability for Violation of Competition Law

The relevance of the study is determined by the need to establish corporate responsibility for breach of legislation. In this regard, this paper is aimed at identifying features of competition and corporate responsibility for breach of competition law. Particular attention is drawn to the case when corporations become monopolists and, in fact, dictate market rules. Consideration of the development aspect of competition law suggests that it largely limits the growth of corporate business and forces corporations to formulate strategies for splitting the business, thereby determining the conduct of business. In the modern world, where business is in many respects globalised, such measures can lead to a decrease in market indicators and form a dependence on the operations of certain corporations in the local market. The leading method to the study of this issue is the modelling method, which allows to consider this problem as a targeted and organised procedure related to the improvement and application of competition law, as well as the protection and development of competition. The novelty of the study lies in the possibility of limiting the activities of a corporation in a market that is occupied by it and where there is no practical competition. The authors consider the mechanism of self-regulation as a source of domestic competition law. The paper determines that self-regulation processes are also subject to state supervision and thus corporate self-regulation becomes an aspect of the regulation of competition enforcement by the state at large. The practical significance of the study is determined by the structural feature of the corporation as a quasi-state mechanism and the regulation of external relations between the state and corporations as tax residents on this basis