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Metal‐Responsive Up‐Regulation of Bifunctional Disulfides for Suppressing Protein Misfolding and Promoting Oxidative Folding
Abstract The stress‐responsive up‐regulation process is a sophisticated biological response to maintain cellular homeostasis. In intracellular anti‐oxidant systems, the expression level of oxidoreductases is up‐regulated under oxidative stress, mitigating oxidative damage on biomolecules and enhancing protein folding capacity. Herein, inspired by the biological system, we developed a synthetic folding promotor whose reactivity is up‐regulated under stress conditions. We conjugated two metal‐binding 1,4,7,11‐tetraazacyclotetradecane (cyclam) ligands and a redox‐active disulfide to obtain cyclam‐SS, whose reactivity can be enhanced under metal‐induced stress. Metal coordination increased the redox potential of cyclam‐SS, activating it as an oxidant. While Cu II ions severely hampered the oxidative folding of substrate polypeptides, cyclam‐SS exhibited bifunctional folding‐promoting properties, i) suppressing Cu II ‐mediated misfolding and aggregation, and ii) harnessing Cu II to enhance oxidative folding. Cyclam‐SS was also useful for disulfide‐bond formation to promote oxidative folding of pharmaceutical and pathological proteins, as demonstrated with proinsulin and superoxide dismutase 1 (SOD1). Furthermore, cyclam‐SS protected cultured cells from copper‐induced stress. Thus, we demonstrated the induction of the stress‐responsive up‐regulation process by a bifunctional folding promotor controlling the folding status of biologically important proteins under metal‐induced stress. The strategy of “stress‐responsive up‐regulation” could aid the development of novel synthetic materials for treating intracellular stress and related disorders.
Kolmogorov–Arnold Networks for predicting carotid intima-media thickness in cardiovascular risk assessment
Correction: of HSD3B1 upregulation via LRH1 sustains estrogen receptor signaling and promotes endocrine resistance in breast cancer
Barriers and strategies to enhance HPV vaccine uptake in adolescents living with HIV and their guardians in Lilongwe, Malawi
The E3 ubiquitin ligase MARCHF8 restricts HSV-1 infection by inhibiting replication of the viral genome
Finite element analysis of the influence of surface layer on frictional wear in a follow-up screw-rod kinematic node in GGS stabilization
Molecular basis of the autoregulatory mechanism of motor neuron-related splicing factor 30
Privileged Chiral Photocatalysts
Abstract Privileged chiral catalysts have transformed asymmetric synthesis, conferring generality to processes that are routinely leveraged in the construction of societally important functional small molecules. Operating in the ground state, these catalysts are conspicuous in their ability to simultaneously regulate reactivity and translate chiral information, often with broad substrate tolerance: this technology continues to expedite chemical space exploration. In stark contrast to the specificity of many enzymatic transformations, this promiscuity affords remarkable latitude for creative endeavour in synthesis. Given the transformative impact that stereoselective photocatalysis has had over the last decade, identifying privileged chiral catalysts that permit reactivity and enantioselectivity to be regulated in excited‐state scenarios has emerged as an attractive but challenging frontier. Providing solutions to address this paradox will require the reactivity/selectivity divide to be reconciled through the validation of chiral scaffolds that effectively operate in non‐ground state environments. Inspired by the venerable treatment by Yoon and Jacobsen entitled “ Privileged chiral catalysts ” ( Science 2003 , 299 , 1691–1693), this mini‐review is intended to survey the conception and evolution of privileged chiral photocatalyst scaffolds, and offer a perspective on emerging contenders.
Identification of candidate gene networks affecting the number of somatic cells count and milk production in Iranian Holstein cows using Genome-wide association study
Visualization of covalent intermediates and conformational states of proline utilization A by X-ray crystallography and molecular dynamics simulations
Donor Engineering for High Performance n‐Type OECT Materials with Exceptional Operational Stability
Abstract Donor–acceptor (D–A) conjugated polymeric mixed ionic–electronic conductors (PMIECs) have been widely used in organic electrochemical transistors (OECTs) due to their structural diversity and the tunability of their frontier molecular orbital (FMO) energy levels. However, the slower development of n‐type materials compared to p‐type ones limits their potential in advanced technological applications. In this study, we design and synthesize a novel thiophene‐based donor building block, 2,3‐di(thiophen‐2‐yl)fumaronitrile ( DTFMCN ), for D–A conjugated n‐type PMIECs through donor engineering strategies. DTFMCN can be easily synthesized from commercially available starting materials via a simple one‐step process. The DTFMCN‐based D–A conjugated polymers, S‐DTFMCN and B‐DTFMCN , exhibit extremely low‐lying lowest unoccupied molecular orbital (LUMO) energy levels and show typical n‐type characteristics. OECT devices based on these polymers demonstrate ultra‐low threshold voltages (6 and 40 mV) and high µ C* values of 13.49 and 13.57 F cm −1 V −1 s −1 , respectively. More importantly, these devices exhibit exceptionally high operational stability; the current retention rate after 168 minutes of operation is 96%, making them one of the most stable n‐type OECT devices reported to date. This study highlights the effectiveness of DTFMCN in improving the operational stability of n‐type OECT devices, offering promising potential for applications in bioelectronics.
Ternary atomized Hollow carbon spheres for high-performance symmetric supercapacitors
Association of protein arginine deiminase 4 with the myosin-9 motor complex
Macromolecule‐Driven Supramolecular Polymerization Induced by Crowding Effects
Abstract Macromolecular crowding plays a crucial role in biological systems by regulating dynamic processes, yet its effects in fully synthetic environments remain largely unexplored. Here, we systematically investigate how excluded volume effects influence supramolecular polymerizations in organic media. We employ various discotic supramolecular monomers that assemble sequentially into polymers and kinetically‐controlled higher‐order aggregates (HOAs) only in the presence of macromolecular crowders. The phase diagram of the supramolecular assemblies reveals a strong dependence on the macromolecule concentration, size, and polarity, which can be tuned to control polymerization. Remarkably, at high crowder concentrations, large condensed and aligned assemblies were observed in dried samples, suggesting a transition to phase‐separated states. By testing different monomers, macromolecules, and solvents, we establish the general applicability and versatility of macromolecular crowding in guiding supramolecular polymerization. This work provides fundamental insights into assembly processes in crowded environments and opens new avenues for applying macromolecular crowding beyond aqueous systems.
Capturing the dynamics of adolescent emotion regulation in anxiety-inducing situations through development and evaluation of a state emotion regulation questionnaire for adolescents
Abstract The development of functional emotion regulation (ER) is crucial for mental health in childhood and adolescence—especially in today’s context of multiple crises, which have led to rising anxiety even in the general population. Although the importance of ER is widely acknowledged, existing assessments have yet to adequately measure state ER, particularly in anxiety-inducing situations. We aimed to develop and evaluate the psychometric properties of the State Emotion Regulation Questionnaire (ERQ State) for adolescents, with a future focus on clinical populations. An online experiment was conducted with 105 German adolescents (M age = 13.5 years, SD age = 2.4), using four types of anxiety-inducing vignettes (social anxiety, general anxiety, specific phobia, separation anxiety) to examine potential correlations with trait anxiety. Confirmatory factor analyses were performed to refine the ERQ State-short item pool, revealing strong support for its theoretical structure in scenarios related to social anxiety (Vignette 1). However, model fit was less satisfactory for the remaining forms of anxiety (separation anxiety, specific phobia, generalized anxiety; Vignette 2). While further refinement and validation are needed, the ERQ State-short appears to be a promising tool for assessing ER in anxious adolescents, particularly in contexts involving social anxiety.
Ubiquitin-specific protease 7-mediated stabilization of discoidin domain receptor 1 drives progression of TP53-Mutant cancers
Dinuclear Au(0) Complex Supported by Tridentate P–Mg–P Ligands
Abstract Despite significant advances in gold chemistry, the synthesis and stabilization of gold centers in a low oxidation state, particularly dinuclear Au(0) species, remain a considerable challenge. In this work, we report the successful isolation of a novel dinuclear Au(0) complex stabilized by tridentate P–Mg–P ligands. Computational studies demonstrate that the Au(0)–Au(0) σ‐bond acts as a two‐electron donor to the Mg centers. Reactivity studies further revealed the complex's unprecedented ability to perform two‐electron reductions on a range of substrates, akin to the behavior of well‐established Mg(I) and Zn(I) dimers.