Psycholinguistic Potential of Political Concepts of the Election Campaign (on the example of the slogan-motto “Army. Language. Faith”)

The aim of the study is a psycholinguistic analysis of the stimulus words (Ukrainian) army, language, faith as concept-forming nominations of the appropriate text concepts in the structure of the slogan-motto (advertising slogan, political slogan) “Army. Language. Faith.” the 2019 election campaign (that is, in the context of a particular discursive practice). Methods of the research. The application of the method of free associative experiment basing on the theory of speech influence allows to interpret the semantics of the analyzed concepts, as well as to establish their closest connections and logical relationships with other concepts. Verbal reactions to a political slogan as a whole and to its individual structural units as concept-forming nominations are interpreted as verbal representations of cognitive features of concepts. Results. The results of the associative experiment are a relevant source of data in order to identify markers of the deep (including subconscious) mechanisms of verbal and non-verbal behavior of individuals, which can be used to form new and transform old political concepts. The presence of intersecting segments in their semantic fields testifies about the partial synthesis of diverse concepts in the recipients’ minds, in which the effect of the psycholinguistic influence of the slogan-motto is increased. The absence of such an intersection is an indicator of the information the general information field of the concepts, which is expressed in the discrete perception of the advertising slogan. Conclusion. In the context of the speech theory influence, the first two stages of implementation the text slogan-motto “Army. Language. Faith.” into mass consciousness (attracting attention to the text and optimization its perception) were successfully implemented. A number of reasons (extralinguistic and linguistic formation, for example, the use of words with abstract, non-specific semantics “language”, “faith”) complicated the implementation of the third stage (acceptance of the content) of the implication of the text. Concept-forming nomination “army”, potentially containing negative semantic components, caused reactions associated with the emergency of cognitive disbalance in the consciousness of individuals. Comparison of the associates of the two stages of the experiment showed that the context of perception of the stimulus words is important for the respondents. Thus, the evaluative connotations of reaction words (in particular, concerning the nomination “army”) in the context of the advertising campaign of P. Poroshenko’s party and outside this context differ significantly.

Kinetic analysis of the partial synthesis of artemisinin: Photooxygenation to the intermediate hydroperoxide

The price of the currently best available antimalarial treatment is driven in large part by the limited availability of its base drug compound artemisinin. One approach to reduce the artemisinin cost is to efficiently integrate the partial synthesis of artemisinin starting from its biological precursor dihydroartemisinic acid (DHAA) into the production process. The optimal design of such an integrated process is a complex task that is easier to solve through simulations studies and process modelling. In this article, we present a quantitative kinetic model for the photooxygenation of DHAA to an hydroperoxide, the essential initial step of the partial synthesis to artemisinin. The photooxygenation reactions were studied in a two-phase photo-flow reactor utilizing Taylor flow for enhanced mixing and fast gas-liquid mass transfer. A good agreement of the model and the experimental data was achieved for all combinations of photosensitizer concentration, photon flux, fluid velocity and both liquid and gas phase compositions. Deviations between simulated predictions and measurements for the amount of hydroperoxide formed are 7.1 % on average. Consequently, the identified and parameterized kinetic model is exploited to investigate different behaviors of the reactor under study. In a final step, the kinetic model is utilized to suggest attractive operating windows for future applications of the photooxygenation of DHAA exploiting reaction rates that are not affected by mass transfer limitations.

Bisindole Alkaloids from the Alstonia Species: Recent Isolation, Bioactivity, Biosynthesis, and Synthesis

Bisindoles are structurally complex dimers and are intriguing targets for partial and total synthesis. They exhibit stronger biological activity than their corresponding monomeric units. Alkaloids, including those containing C-19 methyl-substitution in their monomeric units, their synthetic derivatives, and their mismatched pairs can be attractive targets for synthesis and may unlock better drug targets. We herein discuss the isolation of bisindoles from various Alstonia species, their bioactivity, putative biosynthesis, and synthesis. The total synthesis of macralstonidine, macralstonine, O-acetylmacralstonine, and dispegatrine, as well as the partial synthesis of alstonisidine, villalstonine, and macrocarpamine are also discussed in this review. The completion of the total synthesis of pleiocarpamine by Sato et al. completes the formal synthesis of the latter two bisindoles.

Tetracycline antibiotics

Tetracyclines belong to the first broad-spectrum, well-tolerated, and easy-to-administer antibiotics, which are effective against plague, cholera, typhoid, syphilis, Legionnaire’s disease, and anthrax. Some can also be used to treat malaria, Lyme disease, tuberculosis, Rocky Mountain spotted fever, and leprosy. Humans first encountered these chemical species involuntarily in ancient times, as evidenced from the analysis of bone samples dating back more than 1500 years. Shortly after World War II, they were “rediscovered” at Lederle Laboratories and Pfizer as a result of an intense search for new antibiotics. Their bacteriostatic action is based on the inhibition of protein biosynthesis. Since the structure elucidation by Robert Woodward, Lloyd Hillyard Conover, and others in the 1950s, tetracyclines have become preferred targets for natural product synthesis. However, on industrial scale, they became readily available by fermentation and partial synthesis. Their casual and thoughtless use in the initial decades after launch not only in humans but for veterinary purposes and as growth-enhancement agents in meat production rapidly led to the emergence of resistance. In an arms race for new antibiotics, more and more new drugs have been developed to deal with the threat. In this ongoing endeavor, a remarkable milestone was set by Andrew Myers in 2005 with the convergent total synthesis of (−)-doxycycline, as well as numerous azatetracyclines and pentacyclines, which has inspired chemists in the pharmaceutical industry to discover novel and highly active tetracyclines in recent years. Graphic abstract

The Role of the Lexicon in the Syntax–Semantics Interface

Evidence from the study of verbal argument alternations suggests that the syntactic structure of an event-denoting clause often reflects the structure of the event it denotes, in the sense that parts of the clause refer to aspects of the event. The patterns of such mappings between clause structure and event structure tend to be crosslinguistically uniform. Proffered explanations for these phenomena fall into two distinct theoretical currents. Lexicalists explain these phenomena in terms of the inherent paradigmatic structure of the lexicon, which leads verbs with similar meanings to have similar valence structures. Constructionists see these phenomena as evidence that the syntax itself conveys meaning that composes with the meaning contributed by the verb. The roots of this theoretical split are traced to differing perspectives on polysemy, and a partial synthesis of the two perspectives is proposed.

Synthesis of 13C-Labeled Steroids

Due to the wide spectrum of biological activities of steroids, the detection and quantification of steroidal residues in various biological materials are crucial for drug development, doping prevention, and environmental protection. In addition, the analytical technique of stable isotopic dilution (SID) by Liquid Chromatography-Mass Spectrometry (LC-MS) requires 13C-labeled steroids as standards to provide accurate and reproducible steroid quantification. In this context, the synthesis of 13C-labeled steroids is reviewed. The approaches based on partial synthesis starting from commercially available steroids have been, by far, the most commonly employed strategy.1 Introduction2 Hemisynthesis of 13C3-Labeled Steroids via Partial Degradation of the A Ring2.1 Degradation of the A Ring to an Enol Lactone2.1.1 Introduction of 13C Atom(s) via Claisen Condensation: Turner’s Strategy2.1.2 Introduction of 13C Atom(s) with 13C-Labeled 5-(Diethylphosphono)pentan-2-one Ethylene Ketal Based on the Fujimoto–Belleau Reaction2.2 Degradation of the A Ring and Introduction of 13C Atom(s) with [13C3]-1-(Triphenylphosphoranylidene)propan-2-one3 Construction of the A Ring from an α,β-Unsaturated Ketone with 13C-Labeled 1-Iodo-3,3-(ethylenedioxy)butane as Electrophile4 Construction of the A and B rings: Stork’s Strategy5 Hemisynthesis with Introduction of 13C Atom(s) in the C17 Side Chain6 Conclusion

A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3’S)-Astaxanthin from (3R,3’R,6’R)-Lutein and Lutein Esters via (3R,3’S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms

Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, these approaches have not only provided limited global yields, but its main commercial source also carries several health risks for humans. In this contribution, the one-pot base-catalyzed reaction of (3R,3’R,6’R)-lutein (1) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (2), which in turn is oxidized to (3R,3’S)-astaxanthin (3) with a global yield of 68%. The same oxidation performed with UV irradiation (365 nm) for 5 min provided the highest global yield (76%). These chemical transformations have also been achieved with a significant reduction of the health risks associated with its potential human consumption. Furthermore, this is the first time only one of the configurational isomers has been obtained semisynthetically. The poorly understood formation mechanisms of these two compounds were also investigated using Density-Functional Theory (DFT) calculations. These theoretical studies revealed that the isomerization involves a base-catalyzed deprotonation at C-6’, followed by C-4’ protonation, while the oxidation occurs via free radical mechanisms.

Chlorophyll Breakdown – How Chemistry Has Helped to Decipher a Striking Biological Enigma

How the fall colors arise and how chlorophyll (Chl) breakdown occurs in higher plants has remained enigmatic until three decades ago. Fundamental insights into this fascinating puzzle have been gained, meanwhile, by basic contributions from plant biology and chemistry. This short review is a personal account of key advances from synthetic, mechanistic, and structural chemistry that led to the discovery of the bilin-type Chl catabolites and helped elucidate the metabolic processes that generated them from Chl.1 Introduction2 Discovery and Structure Elucidation of a First Non-Green Chl Catabolite3 Structure Elucidation of Fleetingly Existent Blue-Fluorescent Chl Catabolites4 The Red Chl Catabolite – Key Ring-Opened Tetrapyrrole Accessed by Partial Synthesis5 Synthesis of ‘Primary’ Fluorescent Chl Catabolites by Reduction of Red Chl Catabolite6 Nonfluorescent Chl Catabolites from Isomerization of Fluorescent Chl Catabolites7 Persistent Fluorescent Chl Catabolites and Blue-Luminescent Bananas8 Discovery, Structure Elucidation, and Biological Formation of Dioxobilin-Type Chl Catabolites9 Occurrence, Partial Synthesis, and Structure of Phyllochromobilins, the Colored Bilin-Type Chl Catabolites10 Conclusion and Outlook