Common Motif Research Articles

Photo-induced hydroxypentafluorosulfanylation of alkenes with SF5Cl and oxygen gas and their further derivatization

Fluorinated or fluoroalkylated alcohols are common structural motifs in biologically active molecules, natural products, and pharmaceuticals. However, pentafluorosulfanyl (SF5) alcohols, a unique class of SF5 compounds that serve as synthetically valuable building blocks, are difficult to prepare with current methodologies. In this article, we present a single-step, metal-free, and photo-induced hydroxypentafluorosulfanylation of styrenes or α,β-unsaturated esters/amide, producing a series of structurally diverse pentafluorosulfanyl alcohols with up to 89% yields. This reaction is mild and operationally simple, using molecular oxygen as the hydroxy source. The protocol is suitable for a wide range of alkenes, including natural products and drug molecule derivatives. The formed SF5 alcohol units can be readily converted into diverse functionalized SF5 compounds, such as α-SF5 ketones, SF5 diols, and SF5 cyclic carbonates. The potential applications of these SF5 compounds in pharmaceutical and material sciences are vast, making this research a step forward in the field.

Flexibility and sensitivity in gene regulation out of equilibrium

Cells adapt to environments and tune gene expression by controlling the concentrations of proteins and their kinetics in regulatory networks. In both eukaryotes and prokaryotes, experiments and theory increasingly attest that these networks can and do consume biochemical energy. How does this dissipation enable cellular behaviors forbidden in equilibrium? This open question demands quantitative models that transcend thermodynamic equilibrium. Here, we study the control of simple, ubiquitous gene regulatory networks to explore the consequences of departing equilibrium in transcription. Employing graph theory to model a set of especially common regulatory motifs, we find that dissipation unlocks nonmonotonicity and enhanced sensitivity of gene expression with respect to a transcription factor's concentration. These features allow a single transcription factor to act as both a repressor and activator at different concentrations or achieve outputs with multiple concentration regimes of locally enhanced sensitivity. We systematically dissect how energetically driving individual transitions within regulatory networks, or pairs of transitions, generates a wide range of more adjustable and sensitive phenotypic responses than in equilibrium. These results generalize to more complex regulatory scenarios, including combinatorial control by multiple transcription factors, which we relate and often find collapse to simple mathematical behaviors. Our findings quantify necessary conditions and detectable consequences of energy expenditure. These richer mathematical behaviors-feasibly accessed using biological energy budgets and rates-may empower cells to accomplish sophisticated regulation with simpler architectures than those required at equilibrium.

The Enigma of Ownership of the Balkan Epic

The Balkans, characterized by complex historical, political and cultural dimensions, presents a rich and diverse ethnic, cultural and social picture. This complexity is explored in Adela Peeva's documentary Who Is This Song?, which investigates the contested origins of a folk song claimed by many Balkan nations. The documentary is a truth about the cultural diversity in the Balkans and the difficulty to identify the belonging of almost every cultural product that belongs to the folklore of these parts. This study focuses on Albanian, Bosnian, Croatian, and Macedonian folklore, using phenomenological and comparative methods to uncover common motifs, themes, and narrative structures, as well as differences. The study highlights the rich cultural heritage of the region shaped by various historical influences and contributes to a deeper understanding of the cultural identity of the Balkans. From this research it is concluded that the peoples living in this geographical space have exchanged among themselves over the centuries, so that in modern times, the folklore contents that we have analyzed are so close in terms of theme, motif and narrative structure that if they are not shown in the different language it would be difficult to understand that they belong to some nations. Received: 14 September 2024 / Accepted: 28 October 2024 / Published: 05 November 2024

Genome-wide analysis of the PYL gene family and identification of PYL genes that respond to cold stress in Triticum monococcum L. Subsp. Aegilopoides

Abscisic acid (ABA) is a key plant hormone that regulates plant growth and response to stress . Pyrabactin resistance 1-like (PYR/PYL) proteins are ABA receptors involved in the initial steps of ABA signaling. Triticum monococcum L. subsp. aegilopoides is an important germplasm resource for wheat. In this study, we identified 15 PYL genes from T. monococcum L. subsp. aegilopoides and found that they were distributed across five chromosomes. Based on phylogenetic analysis, we classified these genes into three subfamilies. Members of each subfamily have similar gene structures and contain a common motif. Further analysis revealed that the promoters have multiple hormone-related elements. We found 7, 33, and 49 collinear gene pairs in three different ploidy wheat species (T. urartu, T. turgidum and T. aestivum), indicating that PYL genes are relatively conserved during the process of wheat polyploidization. Additionally, interaction networks and miRNA targets were predicted, revealing interactions between PYL proteins and key components of the abscisic acid signaling network. miR9666b-3p may serve as a central factor in PYL involvement in the abscisic acid network. Through RNA-seq analysis and qPCR validation, three genes (TbPYL2, TbPYL5, and TbPYL12) were found to potentially play a role in cold stress. These findings lay the groundwork for further research on PYL genes in T. monococcum L. subsp. aegilopoides.

Inside Cover Picture

Pyridine and piperidine are common structural motifs in natural products and pharmaceutical compounds, underscoring the importance of their synthesis. Our group has developed chiral spiro‐bicyclic bisborane catalysts that enable the efficient and highly enantioselective reduction of pyridines to chiral piperidines. Subsequent transformations allow the conversion of the piperidine products into bioactive natural products. More details are discussed in the article by Wang et al. on pages 3088—3092. image

Halide Perovskite Induces Halogen/Hydrogen Atom Transfer (XAT/HAT) for Allylic C−H Amination

AbstractAllylic C−H amination has emerged as a powerful tool to construct allylamines, common motifs in molecular therapeutics. Such reaction implies an oxidative path for C−H activation but furnishes reductive amines, inferring mild oxidants’ inactivity for C−H oxidation but strong oxidants’ detriment to products. Herein we report a heterogeneous catalytic approach that manipulates halogen‐vacancies of perovskite photocatalyst and exploits halogenated‐solvents (i.e. CH2Cl2, CH2Br2) as mild oxidants for selective C−H allyl amination with 19,376 turnovers. CsPbBr3 nanocrystals induce cooperative hydrogen‐atom‐transfer (HAT, C−H oxidation, and halogen‐vacancy CsPbBr3−x formation) and halogen‐atom‐transfer (XAT, CsPbBr3−x‐induced solvent reduction) under a radical chain mechanism. Terminal/internal olefins are amenable to forge aromatic/aliphatic, cyclic/acyclic, secondary/tertiary allylamines (70 examples), including drugs or their derivatives.

Violence and apocalyptic notions in Mark 13

Mark 13 is famously known as the most challenging text in the entire Markan gospel. In Mark 13:7–8, the Markan Jesus foretells a tumultuous period marked by wars, rumours of wars, nations in conflict and natural hazards, aligning with common motifs in apocalyptic literature. The language vividly depicts a world in upheaval, emphasising cosmic and earthly disturbances as harbingers of climactic historical moments. The destruction of the temple, announced in Mark 13:2, is subject to both literal and symbolic interpretations, with some associating it with the historical event of the Second Temple’s destruction in 70 CE and others perceiving it as a symbol of the end of an age. Approaching Mark 13 without being triggered by violent connotations is unthinkable. Hence, responsible interpretation is pivotal in addressing such potentially violent connotations, particularly considering contemporary world conflicts. Sensitivity, without compromising the truth of the message of Mark 13, is crucial when considering the text’s impact on war-torn communities. This applies both to a reading that simulates the possible intention of the text within the context in which the Gospel, according to Mark, originated and to a historically informed use of such a reading considering contemporary conflicts. This study aims to employ a historiographical hermeneutic as an investigative tool to contribute a plausible understanding of the present text and avoid utilising this text as proof to promote violence and wars today. Especially, when one considers the recent catastrophes: natural hazards, civil unrest and wars across the world. Some are quick to utilise the Olivet discourse to explain such gruesome activities.Contribution: This study contextualizes Mark 13 within the 1st century CE, focusing on the Second Temple’s destruction in 70 CE. It promotes a sensitive interpretation, avoiding justifications for contemporary violence, and highlights the text’s relevance by drawing parallels between its turmoil and current global conflicts, encouraging ethical reflection.

Elements of Romantic Poetics in Rydbergʼs Work: Continuity and Innovation. The Motif of Journey in Viktor Rydberg’s Poetry

The article is devoted to the motif of journey in the poetry of swedish author of the second half of 19th century Viktor Rydberg (1828–1895). The way has been considered as a metaphor in mythological and folklore texts, and the motif of journey is one of the most common motifs in world literature. It has a special significance for Romanticists, in whose texts the journey symbolizes the process of individual spiritual quest. The similar approach to the metaphorisation of the path is characteristic of Rydberg’s works: the influence of Romantic tradition can be traced in them. The works of swedish poet with the motif of journey and hero-wanderer in the center were analyzed in the article. The role of the motif of journey in the formation of the spiritual apperanance of characters was revealed.

Enantioselective Synthesis of Axially Chiral Allylic Nitriles via Nickel-Catalyzed Desymmetric Cyanation of Biaryl Diallylic Alcohols.

Axially chiral nitriles are common motifs in organic photoelectric materials, biological compounds, and agrochemicals. Unfortunately, the limited synthetic approaches to axially chiral nitriles have impeded their availability. Herein, we report the first nickel-catalyzed desymmetric allylic cyanation of biaryl allylic alcohols for the synthesis of axially chiral nitrile structures in high yields with excellent enantioselectivities (up to 90% yield and >99% ee). This process enables the synthesis of a diverse range of axially chiral allylic nitriles bearing β,γ-unsaturated alcohol moieties. Leveraging the allylic alcohol and cyano groups as versatile functionalization handles allow for further derivatization of these axially chiral frameworks. Density functional theory (DFT) calculations suggest that both steric and electronic interactions play crucial roles in determining the enantioselectivity of this transformation. Moreover, this mild and facile protocol is also applicable for gram-scale preparation of the chiral nitriles.

Enantioselective Synthesis of Axially Chiral Allylic Nitriles via Nickel‐Catalyzed Desymmetric Cyanation of Biaryl Diallylic Alcohols

Axially chiral nitriles are common motifs in organic photoelectric materials, biological compounds, and agrochemicals. Unfortunately, the limited synthetic approaches to axially chiral nitriles have impeded their availability. Herein, we report the first nickel‐catalyzed desymmetric allylic cyanation of biaryl allylic alcohols for the synthesis of axially chiral nitrile structures in high yields with excellent enantioselectivities (up to 90% yield and >99% ee). This process enables the synthesis of a diverse range of axially chiral allylic nitriles bearing β,γ‐unsaturated alcohol moieties. Leveraging the allylic alcohol and cyano groups as versatile functionalization handles allow for further derivatization of these axially chiral frameworks. Density functional theory (DFT) calculations suggest that both steric and electronic interactions play crucial roles in determining the enantioselectivity of this transformation. Moreover, this mild and facile protocol is also applicable for gram‐scale preparation of the chiral nitriles.

Ni-Catalyzed Asymmetric Reductive Arylation of α-Substituted Imides.

α-Aryl imides are common structural motifs in bioactive molecules and proteolysis-targeting chimeras designed for targeted protein degradation. An asymmetric Ni-catalyzed reductive cross-coupling of imide electrophiles and (hetero)aryl halides has been developed to synthesize enantioenriched α-arylglutarimides from simple starting materials. Judicious selection of electrophile pairs allows for coupling of both electron-rich and electron-deficient (hetero)aryl halides in good yields and enantioselectivities.

Stvoření a Setkání. Vybrané luriánské motivy v myšlení Emmanuela Lévinase

The paper presents some common motifs of two thinkers who, despite a historical gap of several hundred years, had common roots in the tradition of Judaism. The notion of the Encounter, as analysed by Emmanuel Levinas, and the cosmogonic process of Creation in Isaac Luria’s system of thought have a common motif in the phenomenon of the socalled “contraction” (Hebrew: tzimtzum). Despite the fact that for the first thinker it is the domain of ethics and for the second the domain of ontology, the act of a certain “self-limitation” or “withdrawal” plays in both cases a foundational role.

Targeting heparanase/heparan sulfate proteoglycans by non‐anticoagulant heparins: Opportunities for innovative therapeutic approaches in sarcomas

AbstractSarcomas are a heterogeneous group of aggressive mesenchymal malignancies. They account for 1% of all tumors in the general population and 15–20% in pediatric age and young adults. Despite differences in histology and pathobiology, the diverse types of sarcomas are traditionally managed with a common multi‐modal approach including surgery, radiotherapy, and aggressive polychemotherapy. Unfortunately, the prognosis for advanced or recurrent disease remains poor. Moreover, the disease rarity and a high cellular, molecular, and genetic/epigenetic heterogeneity make identification of therapeutic targets challenging. Therefore it remains an urgent need to identify effective therapies to improve patients' outcome. Common or peculiar biological motifs including deregulation of growth factor signaling, proangiogenic and promigratory pathways, tumor‐microenviroment interactions, transcriptional and epigenetic machinery, and differentiation program, provide actionable dependencies exploitable for therapeutic intervention. Among these, a deregulated heparan sulfate proteoglycan system due to aberrant expression of key components as well as structural/functional modifications mediated by endosulfatases and the endoβ‐d‐glycosidase heparanase, is emerging as a crucial player in tumor growth and progression and as a valuable therapeutic target across different sarcoma subtypes. In preclinical studies, non‐anticoagulant heparins have been shown to counteract the growth and metastatic dissemination of various sarcoma models according to their heparan sulfate mimetic and anti‐heparanase activities. Heparin derivatives also improved the anti‐sarcoma efficacy of molecularly targeted agents and cytotoxic drugs. In this minireview, we summarize the current knowledge about the interplay between the heparanase/heparan sulfate proteoglycan system and pathways involved in sarcomagenesis and disease progression. We illustrate the current understanding of the mechanisms of action of non‐anticoagulant heparins and the contribution of their anti‐heparanase, anti‐receptor tyrosine kinase, and likely immunomodulatory activities to their anti‐sarcoma effects. Finally, we discuss a few aspects worthy of exploration highlighting how elucidation of mechanisms underpinning antitumor activities of non‐anticoagulant heparin derivatives in the different sarcoma biological contexts may suggest new vulnerabilities and therapeutic approaches.

Radially patterned morphogenesis of murine hair follicle placodes ensures robust epithelial budding.

The bending of simple cellular sheets into complex three-dimensional (3D) forms requires developmental patterning cues to specify where deformations occur, but how positional information directs morphological change is poorly understood. Here, we investigate how morphogen signaling and cell fate diversification contribute to the morphogenesis of murine hair placodes, in which collective cell movements transform radially symmetric primordia into bilaterally symmetric tubes. Through live imaging and 3D volumetric reconstructions, we demonstrate that Wnt and Shh establish radial patterns of cell fate, cell morphology, and movement within developing placodes. Cell fate diversity at different radial positions provides unique and essential contributions to placode morphogenesis. Further, we show that downstream of radial patterning, gradients of classical cadherin expression are required for efficient epithelial rearrangements. Given that the transformation of epithelial discs into 3D tubes is a common morphological motif used to shape diverseorgan primordia, mechanisms of radially patterned morphogenesis are likely highly conserved across evolution.

Dynamics of two feed forward genetic motifs in the presence of molecular noise

Understanding the function of common motifs in gene regulatory networks is an important goal of systems biology. Feed forward loops (FFLs) are an example of such a motif. In FFLs, a gene (X) regulates another gene (Z) both directly and via an intermediary gene (Y). Previous theoretical studies have suggested several possible functions for FFLs, based on their transient responses to changes in input signals (using deterministic models) and their fluctuations around steady state (using stochastic models). In this paper we study stochastic models of the two most common FFLs, “coherent type 1” and “incoherent type 1”. We incorporate molecular noise by treating DNA binding, transcription, translation, and decay as stochastic processes. By comparing the dynamics of these loops with models of alternative networks (in which X does not regulate Y), we explore how FFLs act to process information in the presence of noise. This work highlights the importance of incorporating realistic molecular noise in studying both the transient and steady-state behavior of gene regulatory networks.

Short-term plasticity and context-dependent circuit function: Insights from retinal circuitry

Changes in synaptic strength across timescales are integral to algorithmic operations of neural circuits. However, pinpointing synaptic loci that undergo plasticity in intact brain circuits and delineating contributions of synaptic plasticity to circuit function remain challenging. The whole-mount retina preparation provides an accessible platform for measuring plasticity at specific synapses while monitoring circuit-level behaviors during visual processing ex vivo. In this review, we discuss insights gained from retina studies into the versatile roles of short-term synaptic plasticity in context-dependent circuit functions. Plasticity at single synapse level greatly expands the algorithms of common microcircuit motifs and contributes to diverse circuit-level behaviors such as gain modulation, selective gating, and stimulus-dependent excitatory/inhibitory balance. Examples in retinal circuitry offer unequivocal support that synaptic plasticity increases the computational capacity of hardwired neural circuitry.

May 1968 Protests in France in the Collective Memory of the European Commission Politicians

Introduction. The May 1968 protests are an important place of remembrance in the history of Europe. Methods and materials. The author uses the methods of studying collective memory to analyze the image of the May protests in the collective memory of the European Union. The article analyzes how former members of the European Commission recall the events of 1968 within the framework of The European Commission 1958–1973: History and Memories of an Institution project and how the May protests are woven into the history of European unification. The project was implemented in the early 2000s with the aim of compiling an oral history of the European Union and the European Commission in particular. Analysis. The author summarizes the image of the protests and highlights the general features of the description of the events of 1968. Based on examples of interviews with Fausta Deshormes La Valle, Odile Benoist-Lucie, Franz Froschmaier, and Raymond Barre, the article summarizes a comprehensive picture of the crisis year of 1968, which affected both the political, social, and economic spheres of life in Europe. Results. The memory of the protests, actualized through the interviews, correlates with the first reaction of European politicians in 1968. A significant difference is the selectivity of memories. Politicians in interviews do not recall the violence that the protests caused or the eclecticism of the slogans of the rebel students; the positive image of the protests dominates. The common motif present in most of the interviews is the feeling of young people’s disappointment in the ideals of a united Europe. The May protests are presented as a turning point in the history of Europe, which prompted European politicians to act and further deepen the integration.

Exploration of Tertiary Structure in Sequence-Defined Polymers Using Molecular Dynamics Simulations.

Peptoids are a class of sequence-defined biomimetic polymers with peptide-like backbones and side chains located on backbone nitrogens rather than alpha carbons. These materials demonstrate a strong ability for precise control of single-chain structure, multiunit self-assembly, and macromolecular assembly through careful tuning of sequence due to the diversity of available side chains, although the driving forces behind these assemblies are often not understood. Prior experimental work has shown that linked 15mer peptoids can mimic the protein helical hairpin structure by leveraging the chirality-inducing nature of bulky side chains and hydrophobicity, but there are still gaps in our understanding of the relationship between sequence, stability, and particular secondary or tertiary structure. We present a molecular dynamics (MD) study on the folding behavior of these polymers into hairpins, discussing the differences in structure from sequences with various characteristics in water and acetonitrile, and then compare the handedness preference of common helical motifs between solvents.

Peptide Catalyzed Conjugate Additions to β-Nitroacrylates - Steric Bulk Increases the Reaction Rate.

The organocatalytic conjugate addition of aldehydes to β-nitroacrylates provides direct access to β-ester-γ-nitroaldehydes and, thereby, common structural motifs of many bioactive compounds. However, the deactivation of amine-based catalysts by alkylation with the highly electrophilic nitroacrylates hampers this reaction. Here, we show that the peptide H-Mep-dPro-dGlu-NH2, which is reluctant to under alkylation,catalyzes this reaction at low catalyst loading (0.5-1 mol%) within short reaction times (15-60 min) to yield a broad range of β-ester-γ-nitroaldehydes with high stereoselectivity. Kinetic studies revealed that increased steric bulk on the β-nitroacrylate enhances the reaction rate by hindering catalyst alkylation.

Emerging Trends for the Direct Synthesis of Dithiocarbamates

Dithiocarbamates are common structural motifs in various bioactive compounds, attracting considerable attention due to their wide‐ranging applications in organic synthesis, material science, agrochemicals, and the pharmaceutical industry. Given the significant bioactivity and extensive applications of dithiocarbamates, the continuous pursuit of their efficient and diverse synthetic methods remains critical and urgent. Direct dithiocarbamation reactions can introduce ‐S‐C(S)NR2 group directly into parent molecules, providing shorter, greener, and more practical pathways for the synthesis of organodithiocarbamates. This article offers a comprehensive overview of the latest advancements in direct dithiocarbamation reactions, categorizing them based on the different sources of the ‐S‐C(S)NR2 group, with a particular emphasis on elucidating substrate scope and reaction mechanisms. Additionally, some synthetic limitations and applications of these methods are discussed. This review aims to provide the latest advancements in this field to both general readers and professional practitioners, inspiring innovative ideas for the synthesis of organosulfur compounds.