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Distinct differentiation trajectories leave lasting impacts on gene regulation and function of V2a neurons
Abstract V2a interneurons are excitatory neurons found throughout the hindbrain and spinal cord, two regions that arise from distinct progenitors during embryonic development. Whether this lineage difference shapes mature gene regulation and function is unknown. V2a neurons show plasticity after spinal cord injury and are candidates for cell therapy. We differentiated human stem cells into V2a neurons through hindbrain- and spinal cord-like progenitor routes and profiled them by single nucleus multiomic sequencing. The two lineages showed distinct transcription factor motif enrichment and differentially expressed genes governing axon growth and calcium handling. Inducing V2a transcription factors directly, bypassing developmental patterning, produced a population unlike either lineage, confirming progenitor history is not interchangeable. Using CellOracle and lentiviral knockdown, we identified CREB5 and TCF7L2 as regulators specific to the spinal-like lineage. These results show that progenitor origin shapes V2a identity and reveal new regulators of neural diversity along the anterior-posterior axis.
Outside Front Cover: Catalytic C–F Bond Activation at Room Temperature: Enolate Cross‐Couplings Enabled by [Pd(1‐MeNAP)TFA] <sub>2</sub> and LiHMDS
Single-photon detection in few-layer NbSe2 superconducting nanowires
Abstract Superconducting Nanowire Single-Photon Detectors (SNSPDs) are key building blocks for photonic quantum technologies due to their ability to detect single photons with ultra-high efficiency, low dark counts and fast temporal resolution. Superconducting materials exhibiting high uniformity, large absorption cross-section and atomic-scale thickness are desirable to extend single-photon detection from the near-infrared up to the terahertz regime, where existing material choices are especially constrained. Substrate independence would further open the way to integrating detectors onto functional materials and heterostructures, enhancing performance and enabling proximal readout of a wide range of individual excitations. Here, we pattern the prototypical two-dimensional superconductor niobium diselenide (NbSe 2 ) into few-layer nanowires less than 100 nm wide and demonstrate single-photon detection at 780 nm and 1550 nm. At the same time, the dark-count rate remains below 1 Hz up to the switching current and we achieve a timing jitter below 50 ps. We estimate via a diffusive hot-spot model that materials and geometric parameters would allow a theoretical cut-off wavelength in the millimetre range, assuming state-of-the-art device parameters. Our results open up routes toward quantum-limited detectors integrated into quantum-photonic circuits and quantum devices, with the potential for novel detection capabilities and unprecedented energy sensitivity.
Inside Front Cover: Bimetallic Node Occupied MOF With Glycoside Hydrolase Activity for Efficient Bacterial Biofilm Hydrolysis
CELF2 promotes 4R Tau splicing via nuclear clustering and drives cognitive dysfunction in tauopathy models
Spatially Homogeneous Mg <sub>3</sub> (Sb, Bi) <sub>2</sub> With Suppressed Parasitic Transport Enables Ultrahigh Thermoelectric Performance
ABSTRACT Chemical inhomogeneity widely exists in thermoelectric materials, yet its effects are mainly ascribed to local interface scattering and compositional fluctuations. Here, we show that the spatial connectivity of chemical inhomogeneity governs thermoelectric performance by enabling parasitic transport pathways. In Mg 3 (Sb, Bi) 2 , multiscale Bi‐related chemical inhomogeneity forms spatially connected percolation pathways that deteriorate both the Seebeck coefficient and thermal conductivity. Cyclic pressure sintering disrupts these percolative networks, thereby inhibiting parasitic transport and enhancing phonon scattering. As a result, a high zT of ∼2.08 at 673 K and an exceptional average zT of ∼1.58 over 323–723 K are achieved, placing these values among the highest reported for Mg 3 (Sb, Bi) 2 ‐based materials. Furthermore, a single‐leg device delivers a conversion efficiency of ∼12.1% (Δ T = 410 K). These findings establish the spatial connectivity of heterogeneity as a key parameter governing thermoelectric transport and provide a general strategy for performance optimization.
Stable Full‐Color and Single‐Phase White Emission in a Family of Isomeric Organic Cu(I) Iodides
ABSTRACT Organic Cu(I) halides feature highly designable structures, systematic tunability, and efficient emission; however, simultaneously achieving full‐color tunable emission and single‐phase white emission with thermal‐ and chemical‐stimulated optical responses in organic isomeric Cu(I) halides polymorphs have never been reported. Herein, we synthesized a family of zero‐dimensional organic isomeric Cu(I) iodides of α‐/β‐/γ‐/δ‐/ε‐(ITPP) 2 Cu 2 I 4 , all of which have the same molecular formula and crystallize in monoclinic space group P 2 1 / n . However, due to the different arrangement orientation of [Cu 2 I 4 ] 2− clusters and the surrounding molecular environment, α‐/β‐/γ‐/δ‐/ε‐(ITPP) 2 Cu 2 I 4 exhibits blue, green, yellow, red, and white emission, with an optimal luminous efficiency of 92.4%. Interestingly, α‐/β‐/γ‐/δ‐/ε‐(ITPP) 2 Cu 2 I 4 shows tunable dual self‐trapped excitons emission under different temperatures, making them suitable for optical thermometry with an ultrahigh relative thermal sensitivity of 13.17% · K −1 . Moreover, external chemical stimuli can induce luminescent transformation between different hybrid Cu(I) iodides, which enables us to demonstrate their application in multiple anti‐counterfeiting. Parallelly, hybrid Cu(I) iodides also exhibit efficient x‐ray scintillation with a high light yield of 63500 ± 1200 photons/MeV, and a customizable large‐area flexible paper‐based film has been prepared in situ using an “ancient fabric dyeing process”, demonstrating its application in x‐ray imaging with an ultrahigh spatial resolution of 20.8 lp/mm.
Inside Back Cover: A Cholesterol Analogue for Cell‐Surface Enzyme Display
Vicinal‐Diboron Reinforced [9]Helicene Enables Narrowband Blue Circularly Polarized Emitter With Large Dissymmetry Factor and High Device Efficiency
ABSTRACT Circularly polarized multiple‐resonance thermally activated delayed fluorescence (CP‐MR‐TADF) emitters that simultaneously combine narrowband emission, high efficiency, and pronounced chiroptical activity remain rare because amplification of helicity often compromises the localized electronic structure required for spectral narrowing. Here we report a tetraborated B,N‐embedded [9]helicene, B 4 ONA, constructed through ortho ‐diboron reinforcement of a multiple‐resonance framework. Structural and theoretical analyses reveal that the ortho ‐diboron configuration strengthens helical rigidity and excited‐state confinement, thereby suppressing structural relaxation and vibronic coupling. B 4 ONA exhibits pure‐blue emission at 462 nm with a full width at half‐maximum (FWHM) of 20 nm and pronounced chiroptical activity, reaching a high photoluminescence dissymmetry factor of 5.03 × 10 −3 in the emissive film. Organic light‐emitting diodes (OLEDs) based on B 4 ONA deliver pure‐blue electroluminescence at 464 nm with a FWHM of 21 nm and external quantum efficiencies of up to 34.4%, ranking among the best performances reported to date for blue CP‐MR‐TADF OLEDs. These findings establish ortho ‐diboron reinforcement of high‐order B,N‐embedded helicenes as an effective molecular design strategy for CP‐MR‐TADF emitters.
Triple Framework Isomerism and Efficient Ethane/Ethylene Separation of Single‐Crystal Covalent Organic Frameworks With 2D hcb Sheets
ABSTRACT Constructing triple framework isomerism with atom‐resolution structures is of great significance but remains highly challenging for covalent organic frameworks (COFs). Herein, [3+3] imine condensation of 1,3,5‐trimethyl‐2,4,6‐tris(4‐aminophenyl)benzene with 1,3,5‐triethyl‐2,4,6‐tris(4‐formylphenyl)benzene affords three single‐crystal COF isomers composed of hcb nets. Their AB hcb stacking, double [2D+2D], and triple [2D+2D+2D] crossing entangled structures have been resolved by 3D electron diffraction. Among the three desolvated COFs, GZU‐4a exhibits the highest ethane uptake (100.7 cm 3 g −1 ) and ethane/ethylene selectivity (1.6), enabling one‐step production of high‐purity ethylene (>99.99%) in dynamic breakthrough experiments. The superior and inverse separation performance originates from its rigid non‐interpenetrated framework with optimized pore confinement for strengthened ethane binding. This work not only presents an unprecedented example of triple isomeric COFs with atom‐resolution structures from non‐interpenetration to inclined interpenetration of 2D nets, but also shows an inverse adsorption selectivity for ethane over ethylene, greatly enriching the diversity of COFs.
Inside Back Cover: Recyclable Pt‐Catalyzed Biphase Hydrosilylation on Water: From Functionalized Monomers to Polymer Materials
Solvent Hydrogen Bonding Determines Adsorption Geometry of Trimesic Acid on Cu
ABSTRACT The adsorption geometry of functional molecules largely determines the interfacial behaviour in various applications like catalysis, photovoltaics and molecular electronics. Understanding adsorbate orientation has remained a challenge due to lack of suitable in situ methods, thus hindering controlled device behaviour. Here, a combined tip‐enhanced Raman spectroscopy, density functional theory and molecular dynamics simulation approach elucidates the prevailing controversy about the adsorption geometry of showcase trimesic acid, one of the most widely used functional organic linkers, on Cu. We find that subtle energy differences in adsorbate–substrate–solvent interactions on the scale of 0.25 eV are decisive for the molecular orientation at solid/liquid versus solid/gas interfaces, emphasising the strength of combined theoretical and experimental quantitative in situ nanoscale characterisation for the rational design of functional molecular interfaces.
Network‐Anchored Nanocages Create Weakly Solvating Electrolytes for Subzero Aqueous Zinc Batteries
ABSTRACT Low‐temperature operation of aqueous zinc batteries is fundamentally limited by electrolyte freezing and sluggish interfacial kinetics, originating from strong ion‐solvent interactions. Here, we report a steric‐regulated weakly solvating hydrogel electrolyte enabled by network‐anchored fluorinated Zr‐based metal–organic polyhedra (MOPs). The rigid, hydrophobic nanocage architecture simultaneously anchors Zn 2+ through coordination and sterically excludes active water molecules, thereby diluting the local electrostatic field, lowering the desolvation barrier, and disrupting extended hydrogen‐bond networks to suppress ice crystallization. As a result, Zn||Zn symmetric cells cycle stably for over 3700 h at −40°C, while Zn||MnHCF full cells deliver 65.8 mAh g −1 at −20°C with 82% capacity retention after 350 cycles, and still maintain 24.6 mAh g −1 at −40°C. Spectroscopic, electrochemical, and theoretical analyses reveal that Zr‐based MOPs reconstruct the Zn 2+ solvation shell into a spatially expanded, weakly bound structure that accelerates charge transfer and suppresses parasitic reactions. This work establishes a steric‐architecture design paradigm for engineering weakly solvating electrolytes, offering a robust strategy for aqueous batteries operating under extreme low‐temperature conditions.
White‐Light‐Mediated Imidazole Catalysis Toward Terpene‐Based Thermosets
ABSTRACT Light‐mediated curing of terpene‐derived polymers generally depends on UV irradiation and photoinitiators. We report herein that environmentally friendly limonene‐ and carvone‐derived diepoxides cure with glutaric anhydride under white light through imidazole‐mediated catalysis, without conventional photoinitiators, to afford fully bio‐based thermosets. 1 H NMR reveals a switch in ring‐opening selectivity relative to thermal curing, from predominant exo ‐epoxide opening under heating to preferential endo ‐epoxide activation under white light, evidencing a distinct light‐responsive pathway. The resulting novel thermosets are colorless, transparent and exhibit enhanced thermomechanical properties over thermally cured counterparts, with a Tg of 110°C, tensile strength of 42 MPa, and strain at break of 15%. This strategy is underexplored in terpene‐derived epoxy–anhydride systems and may broaden the scope of terpene‐based thermoset networks.
Outside Back Cover: Rhodium(III)‐Catalyzed Asymmetric Synthesis of Silanes and Cyclopropanes From Diazo Compounds Using Chiral <i>α</i> ‐Pinene‐Derived Indenyl Ligands
Structure‐Guided Redesign of Terminal Deoxynucleotidyl Transferase Enables Scalable Enzymatic DNA Synthesis for Data Storage
ABSTRACT DNA, with its exceptional information capacity and chemical stability, represents a promising material for next‐generation data storage to meet the exponential growth of global digital information demands. Enzymatic DNA synthesis provides a sustainable route to DNA production. However, the practical scalability of the underlying polymerization chemistry has been fundamentally constrained by the low catalytic efficiency and aggregation‐induced inactivation of terminal deoxynucleotidyl transferase (TdT) that is responsible for nucleotide polymerization. Here, we report a structure‐guided enzyme design framework that overcomes these intrinsic limitations by decoupling solubility and catalytic performance in a processive polymerase. Computational redesign of aggregation‐prone regions markedly enhances soluble expression, while targeted active‐site engineering improves catalytic efficiency toward 3′‐ONH 2 ‐dNTPs used in enzymatic DNA synthesis. The resulting TdT variant HL2‐LKI achieves 3.4 g L −1 soluble expression in a 5 L fermenter without fusion tags and exhibits high polymerization efficiency (99.9%) and DNA writing fidelity (98.9%). This redesign reduces enzyme production costs to approximately $0.7 g −1 , nearly seven orders of magnitude lower than the catalog price of commercially available TdT. This work establishes a generalizable strategy for transforming aggregation‐limited enzymatic polymerization reactions into scalable and low‐cost molecular manufacturing processes, thereby advancing the practical implementation of DNA as an information material.
Inside Back Cover: High‐Entropy Catalyst Activated Molecular Oxygen for Oxidative Coupling Under Ambient Conditions
Narrowband Deep‐Red and Near‐Infrared Tetradentate Platinum(II) Complexes for High‐Performance OLEDs With Emission Peaks up to 715 nm and EQEs Over 20%
ABSTRACT Narrowband heavy‐metal phosphorescent complexes have been achieved in the visible region recently, yet such narrowband deep‐red/near‐infrared (DR/NIR) emitters have not been reported. In this study, four new tetradentate Pt(II) emitters ( Pt‐ 1,3 ‐DZF , Pt‐ 2,4 ‐DZF , Pt‐ 1,3 ‐PhCz , and Pt‐ 2,4 ‐PhCz ) are rationally designed by combining donor π‐extension with linkage‐position isomerization based on dibenzo[ b,d ]furan (DZF)‐ and 9‐phenyl‐9 H ‐carbazole (PhCz)‐functionalized triarylamine frameworks. This strategy effectively modulates the emissive excited‐state character and enables narrowband DR/NIR phosphorescence. Vacuum‐deposited OLEDs based on these emitters achieve emission maxima of 670–715 nm, maximum external quantum efficiencies (EQEs) up to 20.4%, and small efficiency roll‐offs at high radiance. Moreover, the full width at half maximums (FWHM) of electroluminescence spectra realize as narrow as 51 nm (0.14 eV), which is comparable to state‐of‐the‐art DR/NIR multiple‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters, highlighting the potential of these Pt(II) complexes for high‐performance narrowband DR/NIR OLEDs.