The accurate computation of high-spin/low-spin gaps remains a challenging task in computational chemistry, with significant implications for both theoretical studies and experimental applications. In this work, we present an exchange-dedicated perturbation theory (EDPT2) that allows an efficient calculation of exchange couplings in magnetic systems. Our approach builds on a previously developed second-order perturbative scheme based on de Loth's formalism but refines the treatment of singlet wave functions by explicitly incorporating ionic determinants in the zeroth-order description. The EDPT2 method is derived from a two-electron-two-center model and can be applied to multispin systems using minimal CAS-generated orbitals. A key advantage of EDPT2 lies in its computational efficiency, with a scaling of <i>N</i><sup>4</sup>, where <i>N</i> is the number of basis functions. Benchmark calculations on diverse test systems demonstrate that EDPT2 achieves high-spin/low-spin gaps with accuracy comparable to the commonly used FIC-NEVPT2 method. Beyond its efficiency, EDPT2 provides valuable information on the mechanisms that govern magnetic exchange. The method allows for a detailed decomposition of second-order contributions, facilitating the identification of dominant exchange pathways. This is exemplified on two bis(nitronyl nitroxide) biradicals, where dynamic spin polarization emerges as the key exchange mechanism. Furthermore, using the example of a trisnitroxide triradical, we demonstrate how the insights from EDPT2 can be used to prepare selective multireference CI approaches. A combined DDCI1 approach with EDPT2-derived corrections is shown to successfully reproduce the experimental doublet-quartet gap.
Body size is a fundamental driver of metabolism, yet it remains unclear whether colonial organisms such as corals conform to the universal ¾-power scaling law. As climate change accelerates metabolic demands, characterizing these scaling relationships is essential to identifying which species are most physiologically vulnerable to environmental shifts. Here, we test whether coral polyp morphological traits can predict aerobic metabolism across a diverse range of reef-building species. We examine relationships between respiration and polyp biovolume, surface area, and corallite width, finding isometric scaling with biovolume and slight positive allometry with surface area, with both exponents close to one. Using median corallite width, we further extrapolate our model to theoretically predict per-polyp respiration for 727 coral species from a publicly available trait database.
Dr. Ritchie writes: "The perspective “Structural Nanocomposites” (Y. Dzenis, 25 January, p. 419) describes a quest for improved structural materials and indicates that composites with nanoscale reinforcements would have “exceptional mechanical properties.” Is this true? Why would reinforcements that are small in size or volume offer any particular benefit over larger-scale reinforcements? As the Perspective correctly asserts, if the composite material is to be used for a small-volume structure, clearly the reinforcements must also be small. In addition, small-volume reinforcements are stronger, as has been known since the early days of research on whiskers (1). In this regard, reinforcement by carbon nanotubes, for example, which are thought of as one of the strongest materials in existence (2), would seem ideal. The problem with this notion is that new materials are not limited by strength, but by resistance to fracture (also known as fracture toughness). It is not by accident that most critical structures, such as bridges, ships, and nuclear pressure vessels, are manufactured from materials that are low in strength but high in toughness. Indeed, the majority of toughening mechanisms mentioned by Dzenis—i.e., crack deflection, plastic deformation, and crack bridging—are promoted by increasing, not decreasing, reinforcement dimensions [e.g., (3)]. Is it any surprise that “results obtained so far are disappointing”?... Dr. Dzenis's reply is included.
Mitochondrial glutathione (mtGSH) supports iron-sulfur cluster (ISC) stability in the electron transport chain (ETC). Here we have investigated the role of the mtGSH transporter SLC25A40 in macrophage activation. SLC25A40 is present in both murine and human macrophages and its expression was increased by LPS treatment. Reducing SLC25A40 expression using siRNA destabilized ISC-rich ETC proteins and elevated mitochondrial and cellular reactive oxygen species (ROS). It also induced expression of the genes Gclc and Gclm, which are involved in GSH biosynthesis. SLC25A40 deficiency also diminished IL-1β and IL-10 production at the transcriptional level in response to LPS. As a result, the production of mature IL-1β was decreased following activation of NLRP3 by nigericin or ATP, with no effect on pyroptosis. Depleting mtGSH with mitochondrially-targeted CDNB phenocopied these defects, whereas supplementation with a cell-permeable GSH ester partially restored pro-IL-1β production. Together, these data identify SLC25A40 as a key regulator that sustains ETC integrity to promote cytokine production, revealing a previously unrecognized role for the SLC25A40-mtGSH axis in coupling mitochondrial redox control to macrophage activation.
Abstract Lipids play crucial roles in immunity and inflammation via controlling immune cell metabolism and function. In particular, phospholipids (PLs), as essential structural elements of biological membranes, critically orchestrate innate and inflammatory responses through coordinating membrane plasticity and cellular signaling. Researches over the past decade have revealed the versatile roles of PL metabolism in innate immunity and inflammation as well as their differential physiological and pathological consequences, highlighting PL metabolites or enzymes as promising potential biomarkers and therapeutic targets. Further unveiling the spatiotemporal characteristics and mechanistic links between phospholipid metabolism, innate immunity, and the development of inflammatory diseases will add new insights into immunometabolism underlying health and diseases, and may suggest new strategies for manipulating PL metabolism toward novel immunotherapy against harmful inflammation and cancer. In this review, we discussed the roles of distinct lipids in innate immunity and inflammation, with particular focus on how phospholipid metabolism and membrane homeostasis are actively reprogrammed during the innate immune response, and how the crosstalk between phospholipids and innate immunity finally orchestrates the outcome of host defense and tissue homeostasis. We also discussed how dysregulation of PL metabolism contributes to pathological processes in inflammatory diseases, such as autoimmune diseases, cardiovascular diseases and cancers, and the potential strategies of restoring PL homeostasis for disease treatment.
Read moreABSTRACT The flexoelectric effect, a polarization phenomenon unrestricted by material symmetry, holds great promise for next‐generation energy harvesting and sensing. However, conventional flexoelectric devices require external mechanical stress, which severely limits their practical applicability. Here, we present a heterojunction‐based dual‐mode flexoelectric nanogenerator that is driven by light and heat, requiring no external mechanical or electrical input. Under illumination (photodetection mode) or temperature variation (thermal response mode), the heterojunction components undergo differential deformation, generating a pronounced interfacial strain gradient that drives strong flexoelectric polarization and flexo‐photovoltaic currents. The photodetection mode demonstrates a broad spectral response from 250 to 600 nm, with a peak responsivity of 2.2 mA W −1 . The thermal response mode exhibits an effective pyroelectric coefficient as high as 7518 µC m −2 K −1 , surpassing conventional pyroelectric materials by over an order of magnitude. By eliminating the need for external stress, this work enables direct coupling among optical, thermal, mechanical, and electrical energies, opening a new avenue for self‐powered photodetectors and thermal sensors based on flexoelectricity.
Read moreContact electrification has been extensively investigated and harnessed, yet quantifying the triboelectrification capacity of liquid phase materials remains elusive due to their non-fixed shape and complex flow dynamics. Here, we report a novel gas-regulated flow strategy to stabilize liquid columns, effectively decoupling fluid kinetics from electrification processes. By optimizing material selection, electrode configurations, and flow regimes, we established a standardized triboelectric series encompassing 50 diverse liquids, including organic solvents and ionic solutions. Our results reveal that liquid-phase triboelectrification is synergistically governed by molecular functional groups, ionic species, and concentrations. Specifically, hydroxyl groups and dilute ion concentrations promote charge transfer, whereas alkyl groups and excessive ions exert a suppressive effect. This study elucidates that liquid-solid electrification arises from a sophisticated interplay of electron transfer, molecular polarization, ion adsorption/screening, which collectively dictate charge redistribution. By providing a quantitative triboelectric matrix, this work facilitates the design of high-efficiency energy harvesters and safer industrial liquid-handling systems, advancing the fundamental understanding of liquid-interface physics.
Read moreABSTRACT Real‐time monitoring of microscopic chemical reactions offers valuable insight into reaction mechanisms, intermediate species, and the reaction kinetics involved. Mainstream electrochemical and chromatographic techniques are often complex, low‐sensitivity, failing to capture transient phenomena or distinguish similar chemical species within the reaction, limiting their accessibility for real‐time and continuing monitoring. Here, high‐resolution interface charge transfer mapping (ICTM) generated by liquid–solid contact electrification is used in situ for continuously monitoring potential chemical changes in the reactions. As liquid reactants slide dropwise over time along an insulating reclined plane, the ICTMs along the sample trajectory over time are recorded and is used to analysis chemical changes within the reactions. By means of time‐resolved ICTM measurements at statically charged dielectric surface, we have probed the dynamic evolution of redox reactions, tracked the organocatalytic reactions, and evaluated the agglomeration state of metal catalysts with a time resolution on the scale of seconds.
Read moreWe aim to investigate the spatial experience of patients with chronic scotomas caused by lesion to early visual cortex, including primary visual cortex (V1) and adjacent extrastriate visual areas. These experiments are conducted as part of an adversarial collaboration testing contrasting theories of consciousness: Integrated Information Theory (IIT) and two Predictive Processing accounts, Active Inference (AI) and Neurorepresentationalism (NREP). The central question is whether lesions to early visual cortex alter the experienced extent of visual space itself, or instead primarily disrupt stimulus content within an otherwise preserved visual space. To address this, we use paradigms in which patients estimate distances or spatial extents that either span a scotomatous region or fall entirely within intact visual field locations. Psychometric functions relating perceived and physical extent are modeled to estimate shifts in the point of subjective equality (PSE). According to IIT, lesions to early visual cortex, including V1 and occipital exstrastriate cortex, should lead to systematic reductions in perceived spatial extent across the scotoma (negative PSE shifts), reflecting a contraction of experienced space. In contrast, Predictive Processing accounts posit that higher-level predictive mechanisms preserve spatial structure despite loss of early input, predicting little or no systematic contraction (with NREP allowing limited context-dependent effects). By quantifying distortions in perceived spatial extent, this protocol aims to distinguish between these competing theoretical predictions.
Read moreHigh field (W-band, 95 GHz) pulsed electron-nuclear double resonance (ENDOR) measurements were carried out on a number of proteins that contain the mixed-valence, binuclear electron-mediating Cu(A) center. These include nitrous oxide reductase (N(2)OR), the recombinant water-soluble fragment of subunit II of Thermus thermophilus cytochrome c oxidase (COX) ba(3) (M160T9), its M160QT0 mutant, where the weak axial methionine ligand has been replaced by a glutamine, and the engineered "purple" azurin (purpAz). The three-dimensional (3-D) structures of these proteins, apart from the mutant, are known. The EPR spectra of all samples showed the presence of a mononuclear Cu(II) impurity with EPR characteristics of a type II copper. At W-band, the g( perpendicular) features of this center and of Cu(A) are well resolved, thus allowing us to obtain a clean Cu(A) ENDOR spectrum. The latter consists of two types of ENDOR signals. The first includes the signals of the four strongly coupled cysteine beta-protons, with isotropic hyperfine couplings, A(iso), in the 7-15 MHz range. The second group consists of weakly coupled protons with a primarily anisotropic character with A(zz) < 3 MHz. Orientation selective ENDOR spectra were collected for N(2)OR, M160QT0, and purpAz, and simulations of the cysteine beta-protons signals provided their isotropic and anisotropic hyperfine interactions. A linear correlation with a negative slope was found between the maximum A(iso) value of the beta-protons and the copper hyperfine interaction. Comparison of the best-fit anisotropic hyperfine parameters with those calculated from dipolar interactions extracted from the available 3-D structures sets limit to the sulfur spin densities. Similarly, the small coupling spectral region was simulated on the basis of the 3-D structures and compared with the experimental spectra. It was found that the width of the powder patterns of the weakly coupled protons recorded at g(perpendicular) is mainly determined by the histidine H(epsilon)(1) protons. Furthermore, the splitting in the outer wings of these powder patterns indicates differences in the positions of the imidazole rings relative to the Cu(2)S(2) core. Comparison of the spectral features of the weakly coupled protons of M160QT0 with those of the other investigated proteins shows that they are very similar to those of purpAz, where the Cu(A) center is the most symmetric, but the copper spin density and the H(epsilon)(1)-Cu distances are somewhat smaller. All proteins show the presence of a proton with a significantly negative A(iso) value which is assigned to an amide proton of one of the cysteines. The simulations of both strongly and weakly coupled protons, along with the known copper hyperfine couplings, were used to estimate and compare the spin density distribution in the various Cu(A) centers. The largest sulfur spin density was found in M160T9, and the lowest was found in purpAz. In addition, using the relation between the A(iso) values of the four cysteine beta-protons and the H-C-S-S dihedral angles, the relative contribution of the hyperconjugation mechanism to A(iso) was determined. The largest contribution was found for M160T9, and the lowest was found for purpAz. Possible correlations between the spin density distribution, structural features, and electron-transfer functionality are finally suggested.
Read moreAbstract Refractory high-entropy alloys (RHEAs) hold promise for applications in extreme environments. However, conventional as-cast RHEAs are constrained by the trade-off between strength and ductility, necessitating time- and energy-intensive post-processing. Here, we propose a streamlined strategy to fabricate RHEAs via laser directed energy deposition (LDED) using elemental powder blends, eliminating the need for post heat treatments. The additively manufactured (AMed) Nb 40 Ta 25 Ti 15 Hf 15 Zr 5 alloy, characterized by a high density of intrinsic edge dislocations introduced during the thermal cycling of the process, demonstrates a remarkable tensile strength of ~497.3 MPa and a uniform elongation of ~6.8 % at 1000 °C, representing a ~ 37.8% and ~61.9% increase, respectively, over its as-cast counterparts. It is found that the intrinsic edge dislocations generated during AM process significantly enhances the alloy’s strain hardening capability at elevated temperatures. Simultaneously, the high density of edge dislocations effectively enhance material deformability through kink band formation and the stochastic nature of dislocation motion. This work presents a cost-effective pathway for the rapid fabrication of AMed RHEAs with an exceptional combination of high-temperature strength and ductility, paving the way for next-generation structural alloys in extreme environments.
Read moreThe Supplementary material contains additional theory (derivation of CP-SCF equations, additional contributions which arise from ECPs and point charges), figures and tables supporting conclusions drawn in the main text.
Read moreThe small gap room temperature semiconductor a-RuCl3 which is known to undergo a Mott-Hubbard transition at low temperatures, is one of the most promising candidates for realisation of an exotic matter form, the quantum spin liquid state, which may have applications in quantum computing. Although being extensively investigated by neutron scattering techniques, electronic study of this system in form of van der Waals heterostructures has been limited to mainly graphene proximity. Here we report a systematic study of planar and tunnelling electronic properties of a -RuCl3 films, where we observe an n-type semiconducting property of a -RuCl3 films at room temperature, with a Mott insulator nature onset below 120K. In constant some of the previous studies, we focus on films of three-layer thickness and below and we find inelastic scattering features, below the Neel temperature of 7-14.5 K, some of which we attribute to single magnon modes. We believe our study electrically confirms preserved low temperature signatures of the bulk zigzag antiferromagnetic order and its single magnon modes within the previously observed continuum in atomically thin film limit. The experimental progress could be a step for future electronic characterisation of quantum spin liquid state in the vicinity of the zigzag antiferromagnetic order as well as the Majorona excitations in a-RuCl3 in tunnelling transistors.
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