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The nonlinear Hall effect (NLHE), an emergent response in systems with broken inversion symmetry, provides a powerful tool for probing topological transport properties. In this context, we investigate copper-substituted lead apatite (LK-99), a material that initially garnered attention for its controversial claim of room-temperature superconductivity. Despite the unresolved nature of its superconducting properties, LK-99’s unique electronic structure characterized by flat bands near the Fermi level and broken inversion symmetry makes it a promising candidate for exploring Berry curvature-driven phenomena, such as the NLHE. Using first-principles density functional theory and an augmented tight-binding Hamiltonian model, we investigate LK-99’s band topology and transport properties. Our calculations indicate that spin–orbit coupling in LK-99 generates multiple Weyl points near the Fermi level, thereby enhancing the Berry curvature distribution by further splitting the bands. Crucially, the absence of inversion symmetry in LK-99 leads to a net Berry curvature dipole (BCD), producing a nonlinear Hall current that scales quadratically with the applied electric field. The nonlinear Hall effect is solely due to the BCD, as the contributions from the Drude weight and quantum metric are zero due to time reversal symmetry. Moreover, we demonstrate that the NLHE in LK-99 can be tuned by varying the direction of the applied electric field, underscoring its potential as a versatile platform for exploring topological transport phenomena and designing next-generation nonlinear electronic devices.more » « less
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Not AvailableAn unmet challenge in radical relay difunctionalization of alkenes is incorporation of two discrete transient radicals in a regiocontrolled manner under transition metal-free conditions. Current protocols typically rely on persistent radicals or organometallic surrogates to trap radical adducts, thereby suppressing the undesired reactions but limiting the diversity. The direct use of two transient radicals remains synthetically elusive. We present a visible-light photoredox catalyzed alkene dialkylation strategy via a kinetically guided conjugative radical-radical coupling. This transition-metal-free approach enables two direct C(sp3)−C(sp3) bond formations across the C=C double bond using alkyl and allyl or benzyl radicals. Mechanistic investigations reveal the radical nature of the process. The success of this approach hinges on kinetically controlled radical addition to alkene substrates and the steric protection of the resulting radical adducts. This mild and functional-group tolerant reaction exhibits broad substrate scope and tolerates structurally complex substrates, highlighting its potential for late-stage functionalization.more » « less
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Abstract Carbosulfenylation of olefins represents an important class of reactions for the synthesis of structurally diverse organosulfur compounds. Previous studies typically yield 1,2‐regioselectivity. In the context of diversity‐oriented synthesis, accessing the regioreversed products is desirable, significantly broadening the scope of these reactions. In this study, we report a nickel‐catalyzed 2,1‐carbosulfenylation of trifluoromethyl‐ andgem‐difluoroalkenes, using free thiols and benzyl bromides as sulfur and carbon sources, respectively. The unusual regioselectivity observed is enabled by a “radical sorting” mechanism. The Ni catalyst activates benzyl bromide to generate a benzylic radical that undergoes hydrogen atom transfer (HAT) with the thiol to form a sulfur‐centered radical. The sulfur radical subsequently adds to the fluoroalkenes, resulting in an α‐fluoroalkyl C‐radical. This radical undergoes SH2 with a Ni–CH2Ar to form a C(sp3)─C(sp3) bond and quaternary center, ultimately producing valuable fluoroalkyl thioethers. Isotopic labeling experiments corroborate a hydrogen atom transfer (HAT) event within the working mechanism.more » « less
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The popularity of smart home devices has led to an increase in security incidents happening in smart homes. A key measure to avoid such incidents is to authenticate users before they can interact with smart devices. However, current methods often require additional hardware. This article proposes STATION, a gesture-based authentication system, an effective gesture-based authentication method built on top of the voice interfaces already available in these smart home devices, without adding new hardware. STATION uses a gesture processing pipeline that identifies Doppler-existing frames and detects the direction of arrival of Reflection to authenticate users in low SNR environments and at longer distances. Furthermore, regarding the nature of gesture-based authentication, this system also supports detecting user liveness, preventing replay and synthesis attacks from remote attackers. The evaluation of STATION shows high accuracy with a false acceptance rate (FAR) of 0.08% and false rejection rate (FRR) of 3.10% for users within 1.5 m of the device.more » « less
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This study probes the lithosphere‐asthenosphere system beneath 155 Ma Pacific seafloor using teleseismic S‐to‐p receiver functions at the Pacific Lithosphere Anisotropy and Thickness Experiment project ocean‐bottom‐seismometers. Within the lithosphere, a significant velocity decrease at 33–50 km depth is observed. This mid‐lithospheric discontinuity is consistent with the velocity contrast between the background mantle and thin, trapped layers of crystallized partial melt, in the form of either dolomite or garnet granulite. These melts possibly originated from deeper asthenospheric melting beneath the flanks of spreading centers, and were transported within the cooling lithosphere. A positive velocity increase of 3%–6% is observed at 130–155 km depth and is consistent with the base of a layer with partial melt in the asthenosphere. A shear velocity decrease associated with the lithosphere‐asthenosphere boundary at 95–115 km depth is permitted by the data, but is not required.more » « less
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Lactones are cyclic esters with extensive applications in materials science, medicinal chemistry, and the food and perfume industries. Nature’s strategy for the synthesis of many lactones found in natural products always relies on a single type of retrosynthetic strategy, a C−O bond disconnection. Here, we describe a set of laboratory-engineered enzymes that use a new-tonature C−C bond-forming strategy to assemble diverse lactone structures. These engineered “carbene transferases” catalyze intramolecular carbene insertions into benzylic or allylic C−H bonds, which allow for the synthesis of lactones with different ring sizes and ring scaffolds from simple starting materials. Starting from a serine-ligated cytochrome P450 variant previously engineered for other carbene-transfer activities, directed evolution generated a variant P411-LAS-5247, which exhibits a high activity for constructing a five-membered ε-lactone, lactam, and cyclic ketone products (up to 5600 total turnovers (TTN) and >99% enantiomeric excess (ee)). Further engineering led to variants P411-LAS-5249 and P411-LAS-5264, which deliver six-membered δ-lactones and seven-membered ε-lactones, respectively, overcoming the thermodynamically unfavorable ring strain associated with these products compared to the γ-lactones. This new carbene-transfer activity was further extended to the synthesis of complex lactone scaffolds based on fused, bridged, and spiro rings. The enzymatic platform developed here complements natural biosynthetic strategies for lactone assembly and expands the structural diversity of lactones accessible through C−H functionalization.more » « less
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