Taras Shevchenko’s Neologism Снігоквіт (Snihokvit): Psycholinguistic, Lexico-Semantic and Cultural Aspects

The article focuses on the study of Taras Shevchenko’s linguistic identity throughthe freeword association test results. The psycholinguistic experiment, “Author Neologisms of Taras Shevchenko,” held in 2019, involved four hundred forty-eight participants aged 14 to 61 y.o. Among them were professors, undergraduate and graduate students from Rivne State Humanitarian University, Lesya Ukrainka Volyn National University, Sarny Pedagogical College, National University of “Ostroh Academy”, Rivne Economic Technological College, National University of Water and Environmental Engineering, Borys Grinchenko Kyiv University,and M. Ocheret Zhytomyr City Humanitarian Gymnasium #23 (Ukraine). The responses of the recipients to the stimulus word снігоквіт/snihokvit (“snow blossom”), Shevchenko’s neologism, have been characterized based on grammatical (paradigmatic, syntagmatic,word-building), meaningful (thematic, reminiscent, reactions-personalities), and formal connections. The following semantic spheres to which the verbal responses belong have been defined: “Names of Flora”, “Natural Phenomena”, “Names of Actions”, “Colour Features”, “Haptic Features”, “Temporal Features”, “Abstract Notions”, aswell as types of responses within the boundaries of associative fields. The specificity of a modern Ukrainian speaker’s perception of the meaningof a neologism taken out of the literary context has also been discovered. The authors have come to the conclusion that the poet created a highly artistic lexical neologism with the help of which he tried to communicate to the reader not only the primary meaningof the word лілея/lileya “white lily” (a flower) but also to provoke aesthetic feelings, and actualizethe imagination about this special flower that is empowered with magic properties in the national linguistic map of the world. All the responses of the considered semantic spheres that belong to the associative fields of the author’s neologism снігоквіт/snihokvit give a better understanding of the lexicon of modern Ukrainian, the psycholinguistic peculiarities of the perception of Shevchenko’s figurative word. They also make it possible to trace specific changes in the conceptual map of the world and its perception

Solid-State Supramolecular Assemblies of Tryptophan and Tryptamine with Cucurbit[6]Uril

The crystal structure of the supramolecular exclusion complexes of cucurbit[6]­uril with amino acid d-tryptophan and its decarboxylation product tryptamine have been determined. The supramolecular self-assembly of the cucurbit[6]­uril with aromatic guests is guided by the combination of ion-dipole, hydrogen bonding, and stacking interactions between indole rings and glycouril groups of cucurbit[6]­uril and leads to the formation of helical nanotubules in the case of tryptophan and stacked columns in the case of tryptamine. The formation of the solid-state complexes is dependent on the type of salt used for solubilization of cucurbit[6]­uril which is explained in terms of the specific coordination mode of cucurbit[6]­uril with magnesium ion

THE STRUCTURE OF THE TETRA-POTASSIUM SALT OF CALIX[4]ARENE DIHYDROXYPHOSPHONIC ACID

The solid-state structure of the tri-potassium calix[4]arene dihydroxyphosphonate salt is presented. In this structure, two potassium cations bridge between layers of dimeric calixarene diphosphonate units and two other potassium cations bridge along the face of the layers. The ubiquitous dimeric association of the calixarenes shows the highest interdigitation value so far observed. As expected, the cations are solvated and are complexed exo with respect to calixarene crown. The octahedral coordination sphere of the potassium cations is formed by two phosphonate groups of the calixarenes and four water molecules. Electrostatic forces represent the major element of interaction in the solid-state system

Carboxylated Pillar[5]arene Meets Medicinal Biguanides: Host–Guest Complexes with Alexidine and Phenformin in the Crystal and Solution/Gas Phase

Here, we discuss crystal and solution/gas-phase complexes of carboxylated pillar[5]arene with two cationic guests, alexidine and phenformin, revealing host–guest and assembly curiosities, the role of hydrogen bonding, and cavity inclusion versus exo-mode binding. We show that the combination of carboxylated pillar[5]arene with bis(biguanidinium) guest alexidine results in the crystallization of open-type supramolecular architecture. This is also the first crystal structure of alexidine ever reported. The crystallization of pillar[5]arene with biguanidinium drug phenformin affects a rare solid-state complex comprising two cavity inclusion modes within the same crystal lattice. The winner in the competition between ethanol molecules and an organic cation (phenformin) for access to the cavity of pillar[5]arene is undecided, visualized as a “snapshot” of these two inclusion possibilities in one crystal structure. Our results demonstrate that carboxylated pillar[n]arenes can be a useful addition to the macrocyclic toolkit for the facilitation of the crystallization of bio(macro)molecules. Moreover, the IM-MS analysis of the precrystallization solutions of pillar[5]arene host and biguanide guests has shown the presence of structures and conformations closely related to those observed in the crystal forms. The most intriguing results obtained for a pillar[5]arene–alexidine complex imply a conformational evolution of the complex over 24 h. The IM-MS analysis complemented by theoretical calculations may be applied to predict and examine the crystallization process of host–guest systems, complementing crystallographic studies

Carboxylated Pillar[6]arene Emulates Pillar[5]arene in the Host–Guest Crystal Complexes and Shows Conformational Flexibility in the Solution/Gas Phase

Despite the thriving interest in the aqueous complexation properties of carboxylated pillar[6]arene, its solid state supramolecular chemistry has remained a mystery. Here, overcoming challenging crystallogenesis, we report the first crystallographic authentication of carboxylated pillar[6]arene in the form of two host–guest inclusion complexes with methyl viologen and pentamidine. The key to the successful crystallization of carboxylated pillar[6]arene is the mixed ionization state of its 12 carboxylic substituents. The deprotonation of several but not all substituents enables intermolecular hydrogen bonding and, as a result, “gluing” and crystallization of pillar[6]arene complexes with the aid of carboxylic-carboxylate, carboxylic-carboxylic, and amidinium-carboxylate supramolecular synthons. Single crystal X-ray diffraction analysis revealed that upon guest inclusion pillar[6]arene adopts a quasi-pentagonal shape rather than the expected hexagonal shape. The squeezed quasi-pentagonal conformation of the six-membered macrocycle is stabilized by two intramolecular hydrogen bonds between pillar[6]arene substituents. Moreover, the distinctive deviation of the macrocycle from hexagonal shape stays operative in the solution/gas phase as concluded from ion mobility mass spectrometry (IM-MS) studies and theoretical calculations. These results provide the first insight into how to gain control over the conformation of flexible pillar[6]arene with a view of solid state design of more advanced supramolecular host–guest structures