Gutenberg College

Abstract The extraordinary advances in carbene (R1–C–R2) chemistry over the past 30 years have been fueled by the introduction of efficient strategies to stabilize the electronic singlet state via p-bonding interactions with the substituents (R1, R2).1–4 In contrast, the lack of similarly efficient approaches to authentic triplet carbenes with appreciable lifetimes beyond cryogenic temperatures hampers their exploitation in synthesis and catalysis.5 Transition-metal substitution represents a potential strategy,6 but thus far metallocarbenes (M–C–R) usually represent high-lying excited electronic configurations of the well-established carbyne complexes (M ≡ C–R). We here report the photochemical synthesis and characterization of persistent triplet metallocarbenes (M–C–SiMe3, M = PdII, PtII). The carbon-centered diradicals exhibit selective reactions in solution and in the solid state, such as carbene C–H insertion and carbonylation. Bond analysis revealed significant stabilization by spin-polarized push and pull interactions along both π-bonding planes, which fundamentally differs from bonding in push/pull singlet carbenes. This bonding model, thus, expands key strategies for stabilizing carbenes towards the open-shell analogues and closes a conceptual gap to carbyne complexes. We anticipate that the introduction of closed-shell transition-metal substituents to triplet carbenes will facilitate their exploitation in chemical synthesis based on the well-developed principles of coordination chemistry.

Abstract The MYB-related transcription factor and partner of profilin (MYPOP or p42POP) is a ubiquitously expressed and understudied protein, recently discovered in restricting oncogenic human papillomaviruses (HPV) and suggested as a tumor suppressor. In this study, we investigate the role of MYPOP on cancer cells. At supra-physiological levels, induced by both plasmid DNA- and messenger RNA-mediated gene transfer, MYPOP emerges as a potent tumor growth inhibitor, capable of inducing cancer cell death while sparing normal cells. Using HPV-transformed cervical cancer cells and normal human epidermal keratinocytes, cell behavior assessments as well as transcriptome analysis revealed MYPOP's specific anti-proliferative and death-inducing impact on cancer cells. We found MYPOP capable of silencing viral and human oncogenes includingE6,E7, andMYC, and of triggering the release of the cancer-killing cytokine interleukin-24. Extending our research to murine Mypop, we observed anti-proliferative effects in mouse melanoma and colorectal cancer cells. Collectively, our findings underscore MYPOP's potential as a selective tumor suppressor in both human and mouse cancer cells, opening a promising avenue for futurein vivostudies.

The article provides a survey of aspect-tense (AT) grams in (North) Slavic and Baltic, with some account of Finnic. More recently developed grams (bound morphology and constructions) are evaluated against a deeper diachronic and larger areal backdrop in order to assess the significance of contact as a factor contributing to convergence of Slavic and Baltic varieties in the AT domain. In fact, the amount of actually converging features related to grammatical oppositions in this area is quite small; these are: (i) Prominent parallels in the strict subject- vs. object-oriented division of perfects in Slavic (mainly Belarusian) rural varieties, which must have been supported by an ancient and very stable Baltic model. (ii) Suffixation patterns of stem derivation in Aukštaitian Lithuanian resembling Slavic secondary imperfectivisation. The reasons for a generally low level of mutual influence between Baltic and Slavic are subjected to some methodological discussion.

The goddess Išḫara is attested early in cuneiform sources, and her cult can be traced back in all regions of the Ancient Near East over a period of more than 2000 years. From this point of view, it is worthwhile to look at her integration into the Hittite pantheon and try to identify changes and continuities in her figure and present some ideas about the circumstances under which the process of integration took place.

A tipografia tem como função primordial anunciar de forma visual ou tátil determinada mensagem, seja ela textual ou sonora, aos leitores e espectadores. A legenda, por sua vez, ganhou extrema relevância no contexto de consumo de conteúdos digitais em diferentes línguas. Diante do exposto, como projetar, então, uma tipografia que englobe aspectos de legibilidade sem comprometer o tempo de leitura e interpretação de textos? Este artigo tem como objetivo a geração de uma lista de requisitos técnicos como resultado de um estudo sobre leiturabilidade e legibilidade à distância. Para isso, foram apresentados conceitos de anatomia tipográfica, características da legenda e definições de leiturabilidade e legibilidade. Foram analisados, por meio de testes visuais, diversas fontes tipográficas produzidas para meios impressos e digitais, esclarecendo as características que contribuem para uma melhor experiência de leitura.

Culture as a complex concept, which lies in the sphere of interests of almost all humanities, is ofparticular interest in the linguistic context. Language is a tool of communication pattern, which expressesthe cultural mentality of the people. Citing the German philosopher R. Konesmann, Kusse H.,Chernyavskaya V. E. believes that the discourse of culture is language, based on various areas of communication.Language, as well as culture, is a complex phenomenon that represents a semantic conceptin all spheres of human life, reflects cultural characteristics and reveals the rich cultural experience ofindividual peoples. In this regard, the linguist analysis of multi-system languages is interesting. The purposeof this article is a comparative study of multi-system languages in a practical and theoretical way.The paper presents different languages comparative study, contrastive research has a theoretical appliedand practical significance. Forms of knowledge about the world have been presented in the concept of«measurement» in different structural languages. One of the tasks of contrastive researches is to reveal thecultural and national similarities and differences of the inner form interlanguage equivalents. The factsof cultural and national similarities and differences of two or more languages in order to detect convergenceand discrepancy are very popular from the point of linguistic universals.Key words: culture, communication, linguistics, interlingual equivalents, idioms.

Synthesis procedures for mix-ligand complexes with a composition of Fe(Htrz)3(1-x)(NH2trz)3x SiF6 · mH2O, 0 ≤ x ≤ 1, m=1,2 are developed. Solid phases are isolated from water-ethanol solutions and studied by X-ray phase analysis, the method of static magnetic susceptibility (temperature range of 100 K to 400 K), IR and Mossbauer spectroscopy (at 200 K and 298 K). The temperatures of direct and inverse transitions are shown to depend on the complex composition.

Nach einer Schmerzbehandlung stellt die Beurteilung von Morphin- und seinen Glucuronidkonzentrationen am Leichenblut hohe Anforderungen an einen forensischen Gutachter. Im vorliegenden Beitrag werden wichtige physikochemische Eigenschaften sowie pharmakokinetische Daten der Analyte zusammengestellt und eine kurze Ubersicht des Wissenstands uber die Pharmakokinetik von Morphin gegeben. Die Durchsicht klinischer Untersuchungen ergab eine grose Bandbreite therapeutischer Morphindosierungen und eine hohe Variabilitat aller pharmakokinetischer Parameter. Auf die Auswirkungen einiger Einflussfaktoren wie Applikationsweg, Applikationsfrequenz, ¶Alter und Allgemeinzustand sowie Leber- und Nierenfunktionsstorungen wird naher eingegangen. Die Vor- und Nachteile analytischer Nachweismoglichkeiten werden erlautert und die Bedeutung des pharmakologisch aktiven Morphin-6-Glucuronids fur die Beurteilung herausgestellt. Die Besonderheiten des Untersuchungsmaterials Leichenblut werden erklart. Mogliche Ursachen fur die Unterschiede der Analytkonzentrationen sowie des Analytenprofils bei unterschiedlicher Provenienz der Proben werden diskutiert. Auf die Bedeutung der unterschiedlichen Blutplasmaverteilung der Morphinglucuronide wird hingewiesen. Die ¶Stabilitat und mogliche Diffusionsvorgange von Morphin und seinen Glucuroniden post mortem stellen in der Regel keine kritischen Punkte bei einer Beurteilung von Konzentrationen im peripheren Leichenblut dar.