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Positional Isomerism Controls Polarity and Nonlinear Optical Properties in One‐Dimensional Hybrid Germanium Halides
ABSTRACT Organic–inorganic hybrid perovskites (OIHPs) exhibit abundant electronic configurations and structural versatility, rendering them promising candidates for photovoltaic and optoelectronic applications. Despite significant progress in optimizing the structural characteristics of organic cations and inorganic frameworks, the role of cations in determining the electronic structure and nonlinear optical properties has long been underappreciated and remains unclear. We report herein three one‐dimensional germanium‐halide perovskites, AGeI 3 , templated by methylimidazolium cation (A = 1‐Mim/2‐Mim/4‐Mim) positional isomers. Controlling the methyl substitution site on the organic cation can engineer polar structures with distinctly different key optical properties, such as second‐harmonic generation (SHG) and birefringence. (1‐Mim)GeI 3 exhibits the strongest powder SHG response of the OIHP crystals (13 × KH 2 PO 4 @1200 nm) and significant birefringence (0.263 @546 nm). Structural analyses and first‐principles calculations reveal that the SHG response originates from synergism between the [GeI 6 ] and π‐conjugated [C 4 N 2 H 7 ] units, with the unprecedented SHG enhancement in (1‐Mim)GeI 3 being primarily attributed to the asymmetric electron distribution arising from N1‐methyl substitution that enables the favorable ordered alignment of the π‐conjugated 1‐Mim. Our findings not only highlight the critical role of cation positional isomers in controlling physical properties in one‐dimensional hybrid perovskites but also establish one‐dimensional germanium‐iodide perovskites as promising lead‐free candidates for nonlinear optoelectronic applications.
Ultrasound viscosity imaging for stratified diagnosis of diabetic peripheral neuropathy: A prospective clinical study
Continental-scale integration of soil metagenomes and organic matter chemistry reveals ubiquitous microbial capacity for chemically-recalcitrant carbon decomposition
Abstract Soil organic matter (SOM) decomposition by microorganisms is a major uncertainty in predicting terrestrial carbon–atmosphere feedbacks, partly because we lack understanding of the microbial diversity involved in depolymerizing different carbon pools across environmental gradients. We address this gap using a continental-scale dataset pairing shotgun metagenomes with high-resolution SOM chemistry, assembling 0.76 Tbp of prokaryotic MAGs (828 genomes) and identifying 66,727 SOM molecules from 47 standardized U.S. soil cores selected using respiration rates from 106 soils. Integrating these datasets reveals widespread microbial potential for depolymerizing chemically-recalcitrant SOM previously considered stable. We uncover complementary metabolic specialization between genera affiliated with two abundant bacterial orders, Rhizobiales and Chthoniobacterales , and an archaeal order, Nitrososphaerales . This metabolic partitioning is consistent across soil depths and activity levels, suggesting coordinated decomposition of complex SOM through distinct but complementary biochemical strategies. The metabolic potential for depolymerization of chemically-recalcitrant compounds is supported by the abundance of these molecules across the soils, as indicated by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS), and by flux balance analysis of metabolic models. Our results show that a substantial portion of ostensibly stable SOM remains vulnerable to microbial decomposition, a mechanism not captured in current Earth System Models.
Remarkable Effect of Odd–Even Spacer in Supramolecular Polymerization and Piezoresponse of Amide‐Functionalized Naphthalene Diimides
ABSTRACT This study reports an unprecedented odd–even spacer‐length effect on the supramolecular polymerization and piezoelectricity of a series of amide‐functionalized naphthalene‐diimide (NDI) derivatives. By varying the number of methylene units ( n = 1–4) in the linker between the NDI‐core and the hydrogen‐bonding amide group, we demonstrate that the parity of the spacer dictates the stability, internal‐order, gelation, and functionality of the supramolecular polymers. Even‐spacer derivatives exhibit significantly higher thermal stability, melting points, and gel‐phase elasticity compared to their odd‐spacer counterparts. Supramolecular polymerization for all derivatives follows a nucleation‐elongation pathway; however, even‐spacer monomers display markedly higher cooperativity and also favor more stable elongation. Molecular dynamics (MD) simulations elucidate the structural origin of these differences: even‐spacer derivatives adopt a tightly packed helical π‐stacking pattern that results in the cancellation of the in‐plane dipoles. In contrast, odd‐spacer derivatives form linear, offset stacking motifs where individual dipoles align and accumulate, leading to highly polarizable supramolecular polymers. This divergence in the internal dipole orientation translates into a dramatic odd–even effect on the piezoelectric dipolar hysteresis. Odd‐spacer derivatives exhibit remarkably high positive piezoelectric coefficients (maximum d 33 ∼ 75 pm/V), whereas even‐spacer systems show much weaker, and rarely reported negative responses (minimum d 33 −15 pm/V).
Metabolic expenditure, neurodevelopment, and weight gain into early childhood after fetal growth restriction
Abstract Fetal growth restriction (FGR) subjects exhibit altered metabolism, with higher metabolic rate due to their small body mass, and by adopting strategies to minimise energy expenditure. We investigated how these metabolic differences develop, or manifest in growth trajectories, after FGR, small for gestational age (SGA) with no evidence of FGR, and normal pregnancies. We curated a unique composite dataset of subjects between 14 weeks of gestation and six years of age. First, we assessed fetal and infant heart rate to assess whether higher metabolic rate persisted postnatally after FGR. Next, as the largest energy expenditure is brain synaptic maintenance, we tested whether FGR infants had lower white matter volume (proxy for synapse number). Finally, we modelled longitudinal body weight into childhood in FGR, SGA, and control groups, and tested for associations with neurodevelopmental scores at 1–2 years. Heart rate at rest was 3.2 beats per minute higher in FGR fetuses and infants (710 subjects), and FGR infants exhibited only 52% the increase in heart rate to a nociceptive procedure (i.e. a physiological challenge) observed in controls. FGR infants had 7 cm 3 smaller white matter volume (270 subjects). Finally, for every − 100 g an individual’s weight deviated below their group’s average (1660 subjects), their motor score was 0.4 points lower (1030 subjects). FGR subjects continue to exhibit metabolic differences long after birth, which may further disadvantage them beyond the initial antenatal insult. Growth trajectories encode information about how FGR is transmitted into suboptimal neurodevelopment, and could identify intervention opportunities.
Structural basis for activation and potentiation in a human α5β3 GABAA receptor
Abstract Anesthetics and anticonvulsants act, in part, through diverse populations of type-A ɣ-aminobutyric acid receptors (GABA A Rs) formed from a pool of 19 subunits. In the hippocampus, α5 subunits primarily coassemble with β3 and, in some cases, γ2, generating numerous subtypes with differential functional and pharmacological properties critical in learning and memory. The stoichiometry, structure, and gating of these subpopulations are poorly understood. Here we show using cryogenic electron microscopy and electrophysiology that the human α5β3 GABA A R predominantly assembles with 2α:3β stoichiometry, though a minority population of 1α:4β indicates multiple assemblies are possible. In a resting-like state, a conserved activation gate and Zn 2+ -coordination at histidines on β3 block ion conduction. Upon GABA binding, global rearrangements release Zn 2+ and open the activation gate in nearly all receptors. The activated receptor is unaffected upon binding the anesthetic etomidate or anticonvulsant topiramate, supporting a conformational selection mechanism of action. This work thus reveals the assembly, activation, and modulation of a GABA A R subtype critical to cognition, providing templates for structure-based drug discovery.
Outside Front Cover: Subsurface Stabilization of Interstitial Pt Atoms on CeO <sub>2</sub> (111): Rethinking Single‐Atom Catalyst Architectures (Angew. Chem. Int. Ed. 25/2026)
A Kansei-mediated protocol for transforming painting palettes into product aesthetics
Leveraging nanoparticle protein corona to advance plasma proteome profiling
Correspondence on the Correction to “Thermally‐Stable Single‐Site Pd on CeO <sub>2</sub> Catalyst for Selective Amination of Phenols to Aromatic Amines Without External Hydrogen”
Transcriptomic insights into exercise-induced trabecular bone microarchitectural adaptations following combined aerobic and resistance training in mice
Abstract Osteoporosis is a prevalent musculoskeletal disorder, rising in incidence and impact as the global population ages. Peak bone mass (PBM), determined by bone mineral density (BMD) during adolescence, is a key determinant of skeletal health and later osteoporosis risk. Exercise enhances BMD, yet its molecular mechanisms remain unclear. This study examined combined exercise effects on bone health in early adult mice using RNA sequencing (RNA-seq) analysis. Nineteen-week-old mice were randomly assigned to control (CON, n=8) or combined exercise (EXE, n=8) groups. The 12-week intervention included aerobic and resistance training, with physical performance tests conducted before and after. Following intervention, tibial bone characteristics were assessed by dual-energy X-ray absorptiometry (DXA) and micro-computed tomography (μCT), while femoral gene expression was analyzed using transcriptomic analysis. EXE mice demonstrated significant increases in grip strength and exhaustion test performance, but not in the rotarod test. Proximal tibial trabecular bone microarchitecture was enhanced in the EXE group, with increased bone volume fraction (BV/TV), trabecular thickness (Tb.Th), and trabecular number (Tb.N), along with a trend toward reduced trabecular separation(Tb.Sp). Transcriptomic analysis revealed 109 upregulated and 551 downregulated differentially expressed genes. Gene ontology analysis highlighted enrichment of terms related to muscle cell differentiation, contraction, and ion regulation. Bone metabolism-related GO Biological Process terms were specifically enriched, with Pax1 and Dcstamp upregulated and Fgf18, Scx, and Scube2 downregulated. KEGG analysis identified eleven significantly enriched pathways, including Calcium signaling, ECM-receptor interaction, and PI3K-Akt signaling. These findings suggest that combined exercise enhances trabecular bone microarchitecture and induces transcriptomic changes involving genes associated with bone development, remodeling, and extracellular matrix organization, providing molecular-level evidence for exercise-induced skeletal adaptation.
A geometric criterion links HIV-1 capsid topography to its biophysical properties and function
Abstract Mathematical models of virus capsid structure are pillars of modern virology, aiding the understanding of viral mechanisms and the design of antiviral interventions. Traditionally, the HIV-1 capsid core geometry is represented as a fullerene lattice, akin to the icosahedral models of spherical viruses in Caspar-Klug theory. However, recent studies revealed that many viral capsids deviate from such idealised lattices, with important functional implication. Here we show that this is the case also for the conical HIV-1 core geometries, in which the hexamer and pentamer boundaries form a pseudo-tiling rather than a perfectly aligned fullerene network. We introduce a triangular geometric criterion that quantifies local deviations of an HIV-1 atomic model from its idealised fullerene backbone. Using this criterion, we present that this difference in geometric organisation between idealised (fullerene) and actual (data-derived) capsid model has implications for the capsid’s biophysical properties. We also discuss the use of the geometric criterion as a predictive tool regarding cofactor binding and implied geometric changes in the capsid surface coupled to the interfacial frustration response. Our results establish a quantitative framework linking capsid geometry, curvature, and biophysical function, offering new perspectives for assembly inhibitor design and lentiviral vector engineering.
Inside Front Cover: Stable Synapse‐Like Memory Switching in N‐Heterocyclic Carbene Monolayers (Angew. Chem. Int. Ed. 25/2026)
DNA-based identification uncovers the illegal trade of sea cucumbers from Brazil
Abstract The illegal trade of sea cucumbers is widespread, driven by high international demand, particularly in Asia, where they are valued as culinary delicacies and for use in traditional medicine. Although domestic consumption in Brazil is limited, illegal harvesting for export is a growing concern, with unregulated fisheries posing a threat to local populations. In 2023, the Brazilian Institute of Environment and Renewable Natural Resources (IBAMA) seized dried sea cucumber specimens at Guarulhos International Airport. Using DNA barcoding with the Cytochrome C Oxidase I (COI) gene, we identified 18 specimens as Holothuria grisea and 22 as Isostichopus badionotus . Although both species are currently listed as “Least Concern” by the IUCN globally, the unregulated nature of this trade raises concerns about potential overexploitation, especially given the ecosystems they inhabit are increasingly vulnerable to habitat degradation and unsustainable practices. Additionally, the absence of H. grisea sequences in public genetic databases required us to collect fresh specimens to complete the analysis, underscoring the need for expanded molecular repositories. Open access to molecular repositories is a cornerstone of modern scientific progress, serving as a critical infrastructure for collaborative research. By providing unrestricted availability of standardized molecular data, these repositories not only prevent redundant investigations and optimize the use of research resources but also reinforce the robustness and reproducibility of scientific findings through independent validation. Furthermore, this democratization of knowledge levels the scientific playing field, enabling institutions of varying sizes and from diverse geographical locations to contribute equitably to the global research endeavor. Consequently, open access to these databases maximizes the return on public investment in science and significantly accelerates the pace of discovery in critical fields such as drug development and materials science. Our findings highlight the effectiveness of molecular tools in identifying illegally traded species, even in degraded forms, and emphasize the importance of stricter monitoring to protect biodiversity.
Diagnostic challenges and Gram-negative pathogen dominance in early- and late-onset neonatal infection in Manila, Philippines
Enantioselective C–H Functionalization Reactions Enabled by Cobalt(III)‐Centered Chiral Pockets
ABSTRACT Due to the difficulty in achieving stereoselective recognition of three‐dimensional functionalization reagents, desymmetrization and (dynamic) kinetic resolution of such complex architectures via transition‐metal‐catalyzed asymmetric C─H functionalization remains highly challenging. Herein, we develop a novel platform for enantioselective C─H functionalization enabled by trivalent‐cobalt‐centered chiral pockets. It achieves two formidable tasks in stereochemical control: (1) the desymmetrization of prochiral biaryls to access enantioenriched axially chiral molecules, and (2) the kinetic resolution of racemic [2.2]paracyclophanes to construct planar‐chiral architectures. Integrated mechanistic and computational studies allowed us to unravel the intricate details of how the cobalt(III)‐centered chiral pockets achieve precise, substrate‐specific recognition within congested 3D molecular frameworks.
Beyond calories: the role of media pressure and body appreciation in shaping time perception of food cues in female adolescents
Arene difunctionalization through an acyl-inserting Smiles rearrangement enabled by N-heterocyclic carbene catalysis
Abstract Arene difunctionalization offers a powerful strategy for the simultaneous installation of two functional groups in a single step. Despite recent advances, ipso / para -selective arene transformations remain underdeveloped. Herein, we report an N -heterocyclic carbene (NHC)-catalyzed radical protocol that addresses this challenge. The process features a unique generation of acyl-inserting Smiles rearrangement, wherein radical Meisenheimer intermediates are intercepted by NHC-bound radicals prior to rearomatization. Subsequent ketone deprotonation regenerates ionic Meisenheimer intermediates, thereby completing the rearrangement and affording 1,4-difunctionalized arenes. This organocatalytic protocol exhibits broad substrate scope, tolerates diverse functional groups, and delivers acylated aniline derivatives in excellent yields (96 examples, up to 98% yield). The synthetic potential is further showcased by a ring-expansion strategy to benzo[ b ]azepines and by late-stage functionalization of drug-like molecules. Mechanistic insights from combined experimental and computational studies shed light on the unique reactivity and the observed excellent site-selectivity.
Grain protein and yield stability study in rainfed durum wheat RILs
Active nitrogen mediated selective ruthenium migration on ceria for high pressure ammonia decomposition
Abstract Precise stabilization of atomic structures under reaction environments remains a central challenge in heterogeneous catalysis. Here, we demonstrate that ammonia (NH 3 ) serves as a chemically active nitrogen source to derive the selective migration of ruthenium (Ru) atoms onto ceria (CeO 2 ) domains, forming a durable atomically dispersed structure. During ammonia decomposition, nitrogen-containing intermediates promote atomic redistribution of Ru and anchor the atoms selectively at CeO 2 , yielding stable Ru-ceria interfaces. The resulting catalyst exhibits high activity in high-pressure ammonia decomposition for hydrogen production, attributed to its lowered activation energy and mitigated hydrogen poisoning. Furthermore, both the catalytic performance and the atomic Ru structure are preserved during long-term high-pressure operation, confirming the exceptional structural stability of the designed configuration. This study establishes active-nitrogen-driven migration as an effective strategy for constructing robust and reaction-friendly catalyst surface.