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Seismic evidence for lower-mantle heat supply beneath the Cordilleran slab window in western Canada
Highly Stereoselective Addition of β‐Borylenamides to Aldehydes Enabled by Late‑Stage Ligand Modification
ABSTRACT The stereoselective synthesis of allylic alcohols bearing both a hydroxyl stereocenter and defined olefin geometry remains a significant challenge. While traditional methods predominantly furnish thermodynamically favored ( E )‐isomers, efficient access to enantiomerically enriched ( Z )‐configured counterparts is severely underdeveloped. Herein, we report an asymmetric addition of β‐borylenamides to aldehydes by rhodium catalysis, enabling the synthesis of ( Z )‐hydroxy enamides with excellent stereocontrol. The requisite β‐borylenamides are stereoconvergently prepared from mixed‐olefin starting materials through directed electrophilic C−H borylation. A key innovation lies in the development of late‑stage modified ligands, readily accessible via direct arylation of phosphoramidites. This modular strategy circumvents traditional de novo ligand synthesis, thereby significantly accelerating the discovery and optimization of privileged ligands. The resulting allylic alcohol products undergo smooth reduction to furnish γ‐amino alcohols with exceptional enantio‐ and diastereocontrol. The influence of the modified ligands on enantioselectivity was elucidated through density functional theory (DFT) calculations.
ATM inhibition potentiates the anticancer activity of pyrazolo[4,3-e]tetrazolo[1,5-b][1,2,4]triazine sulfonamides in colorectal cancer cells in vitro
Abstract Colorectal cancer (CRC) remains a leading cause of cancer-related mortality, with chemoresistance posing major treatment challenges. Here, we investigated the anticancer potential of pyrazolo[4,3- e ]tetrazolo[1,5- b ][1,2,4]triazine sulfonamides (MM129 and MM137) in combination with the ATM inhibitor KU-60,019 in HCT-116 and HT-29 CRC models. Combinatorial treatment significantly decreased cell viability, suppressed proliferation (BrdU and Ki-67), and increased neutral comet and γH2AX-associated DNA damage parameters compared to single-agent treatments. Cell death analyses showed mainly apoptosis-associated changes, while partial protection by NEC-1 suggests that additional non-apoptotic mechanisms may contribute under selected conditions. Our results indicate that MM compounds exhibit measurable anticancer activity in 3D spheroid models and that their combination with ATM inhibition modulates both viability and spheroid morphology, as reflected by changes in ATP levels, core size, and diffusion parameters. Further optimization and mechanistic studies are required to determine the extent and basis of any combinatorial benefit in this context.
Swelling-induced strain-isolation for stretchable and breathable integrated electronics
Tunable Patterning of DNA Origami on Surfaces Using Steric Brushes
ABSTRACT Tailoring the properties of 2D materials through precise control of both local arrangement and long‐range order on surfaces remains a central challenge in materials science. While surface‐assisted assembly of symmetric, non‐interacting DNA origami nanostructures offers a facile route to 2D superlattices, existing approaches typically yield close‐packed arrays with limited control over inter‐origami spacing. Here, we present a tunable and reproducible strategy for regulating the lateral spacing of DNA origami during self‐assembly into macroscopic 2D lattice patterns. By controlling the growth of uniform single‐stranded polynucleotide brushes from the surface of DNA origami, we modulate their effective geometry by introducing longer‐ranged entropic repulsion, which enables precise and adjustable control over inter‐origami distances across macroscopic areas. Using integrated experiments and simulations, we demonstrate how systematic variation of brush length, surface adsorption strength, and brush density can lead to tunable surface patterns across different origami shapes. Overall, this straightforward approach advances the field of DNA‐templated nanofabrication by providing highly programmable templates with precise spatial control. This platform offers a robust foundation for the future integration of functional nanomaterials and the development of organized nanostructures.
Phytochemical characterization and preliminary antimicrobial evaluation of a mono- and sesquiterpene-rich essential oil of Salvia limbata C.A.Mey.
High-quality pure shift NMR spectra by deep learning using multi-spectral input and joint loss functions
Assembly of Protein‐DNA Framework Nanostructures: Structurally Defining Protein‐DNA Interfaces With Aptamer
ABSTRACT DNA and proteins have been extensively explored for self‐assembly of nanostructures. Each has its own advantages and limitations. By integrating them together, protein‐DNA frameworks (PDFs) could potentially combine their advantages while overcoming the limitations associated with each component; thus, providing a huge diversity in terms of structures, functionalities, assembly versatilities, and responsiveness. Though each has been demonstrated to self‐assemble into large structures, it remains a great challenge to engineer well‐structured protein‐DNA interfaces for PDF assembly. Herein, we report a robust and versatile approach to this problem. Specific and high‐affinity protein‐aptamer binding can nicely interface protein and DNA with structural control. A series of bivalent thrombin aptamers were designed to co‐assemble with thrombin into a range of PDFs including discrete triangles and 3D prisms, linear and circular oligomers, 1D chains/ladders, and 2D arrays. The versatility of such a strategy was further demonstrated by the self‐assembly of Plasmodium falciparum lactate dehydrogenase ( Pf LDH)—containing PDFs. In this work, AlphaFold 3, a universal modeling program, dramatically facilitates structural modeling and helps the designs. We believe that such a rational PDF design will find wide applications as multimodal biomaterials integrating the diverse functionalities of proteins and the ease of assembly programmability of DNA.
Role of resveratrol in protection against HEMA-induced gene expression level in cell culture
Supramolecular polymers with water-triggered dense domains enabling mechanical robustness programmability and weather resistance
Breaking π–π Stacking in One‐Dimensional Covalent Organic Frameworks
ABSTRACT Covalent organic frameworks (COFs) constructed from aromatic building blocks typically incorporate specific functional groups to achieve target properties; however, the active role of intrinsic aromatic backbones remains underexplored due to their limited accessibility usually imposed by interlayer π–π stacking. Herein, we report a steric‐hindrance‐driven breaking of interlayer π–π stacking in one‐dimensional (1D) COFs built from sterically enforced non‐coplanar monomers, thereby rendering the accessibility of aromatic domains and enabling superior adsorption performance, as exemplified by I 2 uptake. Two COFs, TFPE‐MDA, and TFPB‐MDA, are assembled via interlayer van der Waals stacking, where the aromatic moieties orient toward the pore channels exposing the backbone π electrons; electron population analysis verifies that this packing does not perturb the π‐electron distribution. Iodine‐vapor adsorption measurements show high I 2 uptake capacities of 4.80 and 5.61 g·g −1 for TFPE‐MDA and TFPB‐MDA, respectively. FTIR, Raman, and XPS characterizations combined with theoretical calculations confirm I···π interactions between I 2 and the accessible π electrons of aromatic moieties in the COF frameworks. This study provides a novel design strategy for high‐performance COF materials by utilizing sterically enforced non‐coplanar monomers for breaking the commonly observed interlayer π–π stacking, thus enabling the access and utilization of the intrinsic π electrons in COF backbones.
Novel oxygenscan parameters differentiate unique hemolytic and inflammatory profiles associated with sickle cell disease genotypes
Rank-guided learning accelerates automated enzyme engineering
A modelling study of nonlinearity of the cross-shore flow under breaking waves
Abstract A new process-based modelling framework is used to simulate wave-driven flows over a bar in the large-scale SINBAD and LIP11-1C experiments, representing high- and low-wave conditions, respectively. The framework couples an open-source Boussinesq wave model with a one-dimensional vertical (1-DV) column model. Model-data comparisons show good model skill, with discrepancies less than 10 $$\%$$ for waves and hydrodynamics, providing a robust basis for analysing higher-order velocity moments. The corresponding results demonstrate that the cross-shore evolution of the free-stream velocity skewness and asymmetry depends strongly on the breaker type, especially in the surf zone. In both tests, the skewness and asymmetry increase during shoaling. Under a spilling breaker, the intrawave velocity shapes reach peak nonlinearities near the breaking point and then decay gradually through the surf zone. In the plunging breaker, peak nonlinearities occur around the bar crest, decrease sharply at the bar crest, and recover within the splashing and plunging points. Inside the surf zone, the velocity signals evolve toward a strongly skewed-asymmetrical form. A very consistent pattern is found in the vertical direction across all cross-shore regions. The velocity skewness systematically increases towards the bed, while the asymmetry decreases, resulting in a more skewed, less asymmetric near-bed velocity. Boundary-layer filtering, phase shift, and undertow contribute to the velocity transformation inside the wave boundary layer. The bispectral analysis shows that, despite spectral energy decay with depth, strong triad coupling and a coherent biphase pattern persist, and at some locations, intensify within the wave boundary layer, demonstrating breaking influences on the re-organised harmonic interactions rather than making the flows random. These associated findings imply that sediment transport formulations based on free-stream skewness and asymmetry may misrepresent near-bed sediment transport.
Quantum state-to-state reaction dynamics of F + HD → HF + D via a single partial wave shape resonance state
Engineering Solvent–Anion Interactions via Asymmetric Ethers for 200 Wh Kg <sup>−1</sup> Low‐Temperature Anode‐Free Sodium Pouch Cells
ABSTRACT Achieving highly reversible Na plating/stripping is crucial for the stable operation of low‐temperature anode‐free sodium metal batteries (LT‐AFSMBs), yet simultaneously realizing ultra‐high Coulombic efficiency (CE) and long‐term durability, accompanied by high energy density, remains a formidable challenge. Herein, by regulating the molecular side chain, we design an asymmetric chain‐like ether solvent that elegantly balances weak Na + ‐dipole and strong anion‐dipole interactions. This rationally tailored electrolyte fosters an anion‐rich Na + coordination environment, which significantly lowers the desolvation barrier and drives the formation of a robust, anion‐derived solid electrolyte interphase with rapid interfacial dynamics. Consequently, the optimized electrolyte delivers an unprecedented average CE of 99.96% over 500 cycles at −20°C. Remarkably, even under stringent conditions of an ultra‐high cathode loading (28.05 mg cm −2 ) and areal capacity (2.48 mAh cm −2 ), the LT‐AFSMBs retain 85.9% of their initial capacity over 600 cycles at −20°C. Moreover, practical Ah‐level anode‐free pouch cells demonstrate stable operation for 300 cycles, yielding a high energy density exceeding 200 Wh kg −1 (based on the mass of entire pouch cell). This paradigm‐shifting solvation strategy provides a highly viable and scalable blueprint for the next‐generation, extreme‐temperature energy storage systems.