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Boolean Logic‐Based Control Over Recombinant Protein Biomaterial Degradability and Therapeutic Delivery
ABSTRACT Recombinant protein‐based biomaterials offer exciting opportunities in materials design and controlled therapeutic delivery. Though their precursors can be readily synthesized with near‐perfect monodispersity and sequence specificity through scalable fermentation processes, recombinant protein materials have yet to achieve the same level of multi‐stimuli‐responsiveness as their synthetic counterparts. Integrating cutting‐edge tools from chemical biology, we autonomously compile topologically specified protein crosslinkers that can be degraded following user‐programmable Boolean logic. Covalent step polymerization of these linkers into protein hydrogels yields smart materials whose cargo (e.g., bioactive proteins, cellular therapeutics) can be liberated following bulk degradation in response to user‐specified input combinations. Demonstrating the versatility of this approach, we release fluorescent protein mGreenLantern following all 17 possible YES/OR/AND logic outputs in response to a 3‐input protease operator set, deliver epidermal growth factor following advanced biocomputation while maintaining native bioactivity, and showcase multiplexed delivery of living cells, all from fully recombinant protein‐based hydrogels. Incorporating advanced intelligence into protein biomaterial responsiveness, we anticipate these methods will dramatically expand potential applications in tissue engineering and precision medicine.
Elasticity of a polymer chain with deformable bonds under fixed extension and constant force
The force–extension response of a polymer chain provides a direct link between molecular conformations and mechanical behavior. Motivated by directional control conditions commonly encountered in single-molecule stretching, we investigate the elasticity of a polymer chain with deformable bond lengths and bond angles in fixed-extension (FE) and constant-force (CF) ensembles, where the extension is defined as the chain’s end-to-end distance projected along the pulling direction. We formulate both ensembles in terms of this projected extension and express their partition functions in transfer-matrix form. Exploiting the resulting structural similarity, we develop a unified computational framework that enables a direct comparison of their finite-chain responses. We show that the FE–CF difference is a finite-chain effect that decreases with increasing force and chain length. We further establish quantitative criteria for the onset of practical ensemble equivalence over finite force ranges and examine their dependence on bond stretching and bond-angle coupling. Applied to realistic carbon-backbone chains, we show that FE-like and CF-like responses become practically equivalent at experimentally relevant chain lengths in the higher-force regime probed by atomic force microscopy, whereas finite-chain ensemble differences remain appreciable in the lower-force regimes accessed by optical and magnetic tweezers. In the long-chain regime of practical equivalence, the semianalytical deformable freely rotating chain (dFRC) model proposed in our previous work [J. Zhu and L. Brassart, Phys. Rev. Lett. 134, 218101 (2025)] provides an accurate reduced description of the full statistical-mechanical response. These results clarify how ensemble choice, finite-chain effects, and local bond deformations jointly shape single-chain elasticity and provide a framework for interpreting and modeling single-chain stretching experiments.
Electric Field‐Empowered Nanozymes: From Passive Adaptation to Active Precision Therapy
ABSTRACT The clinical translation of nanozymes is hindered by the passive and uncontrollable catalytic properties, necessitating active and precise spatiotemporal regulation. Inspired by the electrostatic preorganization theory of efficient natural enzymes, this review provides a systematic analysis of electric field‐regulated nanozymes. Compared to conventional physical stimuli, this approach offers a tunable and complementary framework for active precise therapy. Diverse electrical input modes provide adaptable driving forces for precisely regulating nanozyme catalysis across various biomedical scenarios. Furthermore, at the atomic scale, the underlying mechanisms are elucidated, demonstrating how the electric field inputs optimize the d‐band center, surface charges, band structure, and active sites to promote substrate adsorption and lower reaction energy barriers, thereby enhancing the catalytic effect. To maximize electric field‐nanozyme coupling, design principles for a complete charge pathway are distilled: optimizing intrinsic field response, directional charge rectification, and achieving low‐loss transport. Subsequently, the applications of electric field‐regulated nanozymes in precision therapy are summarized, including on‐demand spatiotemporal activation, quantitative dosage regulation, and active microenvironment remodeling. Finally, this review highlights the immense potential of interdisciplinary integration in overcoming the biosafety and mechanism bottlenecks of this regulation strategy. These insights provide a new perspective for advancing electric field‐regulated nanozymes toward precision therapy.
Ensemble density functional theory of excited states: Exact <i>N</i> -centered formalism and practical opportunities
Ground-state electronic structure calculations using Kohn–Sham density functional theory (KS-DFT) offer an unprecedented balance between efficiency and accuracy, now paradigmatic to the fields of quantum chemistry and condensed matter physics. KS-DFT can be extended to model electronic excitations through density mapping onto a non-interacting ensemble state in which, unlike in thermal theories, the weights assigned to the excited states vary independently. Ensemble DFT (eDFT) has lately become a vibrant area of research thanks to its numerous appeals, such as the adequate treatment of multiple excitations for which the widely used time-dependent extension of DFT struggles. Recently, an enlarged type of ensemble, referred to as a N-centered (Nc) ensemble, has been introduced to describe within the same unified formalism both neutral and charged electronic excitations. This perspective paper provides a detailed exposition of exact Nc-eDFT, with a comprehensive review of its formal developments. To cut practical computational tools out of the exact theory, three original strategies are presented, complementing existing approaches. The first one, related to the design of ensemble density-functional approximations, consists in recycling regular ground-state functionals by dressing them with a weight-dependent scaling function deduced from exact properties of eDFT. We then explore quasi-degenerate formulations of ensemble density-functional perturbation theory, suggesting alternative definitions for the ensemble Hartree, exchange, and correlation energies, individually, and paving the way toward robust orbital-dependent eDFAs. Finally, we revisit and generalize the concept of quantum bath for an ensemble of non-interacting states, laying the foundations of an in-principle exact (in the sense of lattice eDFT) quantum embedding theory of excited states.
Recent Advances in Ferrite‐Based Materials for Biomedical Applications: A Comprehensive Review
ABSTRACT Ferrite‐based nanomaterials have evolved from simple magnetic contrast agents into sophisticated, multifunctional platforms capable of actively regulating biological microenvironments. This comprehensive review critically examines the recent advances in the rational design of spinel and hexagonal ferrites, elucidating the fundamental structure–property–bioactivity relationships that govern their biomedical performance. We explore how atomic‐level engineering, specifically cation distribution, defect modulation, and morphological anisotropy, can be manipulated to tailor magnetic susceptibility, catalytic activity (nanozymes), and specific absorption rates (SAR) for hyperthermia. Beyond traditional applications in MRI and drug delivery, we highlight emerging frontiers including viscosity‐independent magnetic hyperthermia, ROS‐mediated antimicrobial therapy, and magnetic tissue engineering (Mag‐TE). Crucially, this review addresses the widening translational gap between high‐performance laboratory prototypes and clinical reality. We critically analyze the barriers impeding commercialization, such as the discrepancy between colloidal and intracellular heating efficiency, the complexity of protein corona formation, and the challenges of scalable, GMP‐compliant synthesis. Finally, we propose a future roadmap integrating AI‐driven material discovery and green chemistry to develop next‐generation magnetotheranostic systems, positioning ferrite nanoplatforms as central components in the future of precision medicine.
Quantifying pressure effects on the THF hydrate–water interfacial free energy at coexistence conditions: A computer simulation study
In this study, the tetrahydrofuran (THF) hydrate–aqueous interfacial free energy, γhw, is determined along the univariant two-phase coexistence line of the THF hydrate from molecular dynamic simulations. In particular, we determine γhw at 100, 250, and 1000 bar and at the corresponding coexistence temperatures. γhw is directly evaluated from simulations using the mold integration–host methodology, which is an extension of the original mold integration method. Water and THF molecules are described using the well-known TIP4P/ice model and a rigid version of the TraPPE model, respectively. This study is a natural extension of our previous studies, where the same model combination was used to describe the univariant two-phase dissociation line of the THF hydrate in a wide range of pressures [J. Algaba et al., J. Chem. Phys. 160, 164718 (2024)] and to calculate the THF hydrate–water γhw value at 500 bar and the corresponding coexistence temperature [M. J. Torrejón et al., J. Chem. Phys. 161, 064701 (2024)]. The results obtained in this study show excellent agreement with the only experimental data reported in the literature, 24(8) mJ/m2. This is the first time that the THF hydrate–water γhw is predicted along the univariant two-phase dissociation line of the THF hydrate. Our results suggest that there exists a minimum of energy at intermediate-low pressures and, in general, the γhw does not change significantly with the pressure in the range considered in this study. Once again, it is confirmed that the mold integration–host technique can be used to predict directly and accurately the hydrate–water γhw for hydrates with a sII crystallographic structure.
Coupled Ionic Conduction Loss and Dipole Polarization Loss in Atmospheric Water Harvesting Foams for Electromagnetic Wave Absorption
ABSTRACT Water, an abundant resource with approximately 1.3 × 10 16 liters present in the atmosphere and essential for sustaining life, has long held untapped potential for electromagnetic wave absorption (EWA) due to persistent technical challenges, including difficulties in encapsulation, impedance mismatch, and restriction on a single loss mechanism. To address these limitations, this study develops a multi‐phase system via atmospheric water harvesting (AWH), wherein surface tension and capillary action confine inorganic solution to foam surfaces, forming ultrathin liquid films that enable synergistic interaction among the air/water/polymer phases and enhance impedance matching. Experimental results reveal that, within the temperature range of 283–323 K, CaCl 2 ‐PI@H 2 O attains a minimum reflection loss ( R L ) of −44.6 dB at 4 mm (30% RH ‐ 40% RH), effective absorption bandwidth (EAB) perfectly covers the X band (7.4–12.6 GHz). Whereas LiCl‐PI@H 2 O achieves an R L of −40.4 dB at 4 mm (60% RH ‐70% RH), EAB remarkably broadens to 8.4–18.0 GHz. The key innovation lies in the incorporation of water into a confined salt‐solution film, handling the inherent impedance mismatch and single‐loss mechanism limitation of water as an absorbing medium, thereby offering a novel and promising strategy for fabricating high‐performance liquid‐based EWA materials.
Capturing electron correlation at mean-field cost: Assessment of i-DMFT and the underlying correlation conjecture
Accurately treating strong electron correlation in quantum chemistry typically requires multireference wave function methods with steep computational scaling. The recently proposed i-DMFT method promises near configuration–interaction accuracy at mean-field cost by invoking an empirical linear relation between correlation energy and entropy (Collins’ conjecture), whose validity remains unclear. We systematically assess this relation across a range of di- and polyatomic molecules, including diverse bond types, third-row elements, different types of geometric distortions, and excited states. We find that the conjectured linearity holds for bond-breaking processes dominated by electron redistribution within orbital pairs but breaks down for heterolytic dissociation and excited states. In simple molecules, i-DMFT provides a reasonable description of total energies but does not reliably reproduce reduced density matrices or individual energy components. It further degrades in more complex cases, such as ethylene. Based on these results, we formulate criteria for the validity of the conjecture and outline implications for entropy-based reduced density matrix functionals.
An Injectable Magneto‐Responsive Periosteum Reprograms Neutrophil Extracellular Trap Formation for Osteomyelitis Treatment
ABSTRACT Osteomyelitis caused by methicillin‐resistant Staphylococcus aureus (MRSA) biofilms presents significant therapeutic challenges due to antibiotic resistance and persistent bacterial presence. Inspired by the natural periosteum structure, we developed an injectable biomimetic periosteum through thiol‐click chemistry—a hydrogel loaded with NiSr MOF@Mem nanocomposites(NiSr MOF@Mem Gel). This system not only serves as a physical barrier covering bone defects but also, under alternating magnetic field (MF) activation, synergistically executes chemodynamic therapy, controlled antibiotic release, and immunomodulation. In vitro studies demonstrated that this biomimetic periosteum activates NADPH oxidase‐dependent ROS bursts under MF, driving PAD4‐mediated histone H3 citrullination and thereby inducing neutrophil extracellular trap (NET) formation. This process relies on the classical ROS/PAD4 signaling axis, as confirmed by the PAD4 inhibitor Cl‐Amidine significantly suppressing NETosis. Functional assays verified that the system, via NET induction, exerts potent synergistic antibacterial effects against both planktonic and biofilm‐embedded MRSA. In a rat osteomyelitis model, the biomimetic periosteum combined with MF treatment significantly reduced bacterial load in bone tissue and effectively promoted bone repair by modulating the immune microenvironment. This study presents a novel strategy of using a magnetically responsive biomimetic periosteum to remotely regulate innate immunity for biofilm eradication, offering an integrated solution for the synergistic treatment of osteomyelitis.
Voltage-tunable nonequilibrium dispersion interactions
We develop a nonequilibrium Green’s function theory for dispersion interactions between two nanostructures, each an open quantum system driven into a nonequilibrium steady state by an applied bias voltage. Starting from the two-particle nonequilibrium Green’s function, we derive a general expression for the interaction energy in terms of the polarization propagators of the individual systems. The interaction energy admits a physically transparent decomposition into charge noise and charge dissipation contributions, providing a fluctuation–dissipation interpretation that generalizes the equilibrium London picture. Model calculations for coupled molecular junctions demonstrate that the applied voltage can enhance the attractive dispersion interaction by nearly an order of magnitude relative to equilibrium. In thermal equilibrium, the dispersion interaction is universally attractive, irrespective of the specific form of the nanostructure Hamiltonians or their coupling to reservoirs. Out of equilibrium, we introduce a generalized Kubo–Martin–Schwinger ratio that parameterizes the departure from detailed balance. We show that, in contrast to equilibrium, nonequilibrium conditions can lead to a repulsive dispersion interaction. Finally, we discuss the conditions under which population inversion in the electronic leads can drive a sign reversal of the dispersion interaction.
Resolving Heterogeneity of Targeted Lipid Nanoparticles Through Solution‐Based Biophysical Analyses
ABSTRACT Targeted lipid nanoparticles (tLNPs) enable cell‐specific nucleic acid delivery through covalent attachment of targeting ligands that drive receptor‐mediated LNP uptake. tLNPs are potentially promising for pregnancy‑associated applications where precise delivery is required to minimize maternal toxicity and protect fetal health. Yet, rational tLNP design is limited by an incomplete understanding of how physicochemical properties influence biological performance. Traditional analytical methods report only ensemble‐averaged properties, leaving the nanoscale heterogeneity of tLNPs unresolved. Here, we utilize asymmetric flow field‐flow fractionation integrated with in‐line UV spectral analysis, light scattering, and synchrotron small‐angle X‐ray scattering (AF4‐UV‐DLS‐MALS‐SAXS) to resolve ligand‐dependent tLNP subpopulations that differ in size, shape, composition, and relative abundance. Protein conjugation preserves the internal lipid–RNA nanostructure of base LNPs but substantially increases particle heterogeneity, particularly for larger and multivalent ligands. Despite increased heterogeneity, tLNPs functionalized with higher‐avidity ligands achieve more effective targeted placental RNA delivery in mice. Chemometric SAXS analyses reveal that only SAXS‐resolved tLNP subpopulations, not ensemble‐averaged parameters, correlate with targeted placental transfection in vivo, whereas bulk physicochemical metrics more strongly associate with nonspecific hepatic delivery. Together, this work harnesses a separation‐coupled biophysical platform to resolve previously inaccessible tLNP subpopulations and provides insights to inform rational engineering of next‐generation targeted RNA therapeutics.
Improving NMR cryoporometry with octamethylcyclotetrasiloxane: From network models to accurate thermodynamic parameters
Nuclear magnetic resonance cryoporometry is capable of probing large-pore materials with pore sizes ranging from tens to thousands of nanometers. Achieving higher spatial sensitivity requires probe liquids with large solid–liquid interfacial energies, which are often poorly known. A representative example is octamethylcyclotetrasiloxane, which has attracted considerable interest for thermoporometry applications despite the wide scatter in the thermodynamic properties reported in the literature. In this work, we present an experimental approach for accurately determining these properties by exploiting recent advances in the description of solid–liquid equilibria in confined systems. The two proposed strategies provide highly consistent results and can be readily extended to other liquids with unknown thermodynamic properties.
Entropy‐Driven Electrolyte Design for Lithium Metal Batteries: Achieving Interfacial Stability With Fluorinated Fullerene Nanoparticle Additives
ABSTRACT Lithium metal batteries are highly attractive for next‐generation high‐energy‐density storage, and ether‐based electrolytes such as LiFSI/DME are particularly promising for high‐rate operation because of their low viscosity, high ionic conductivity, and favorable compatibility with Li metal. However, current electrolyte optimization strategies still rely mainly on small‐molecule additives that regulate bulk solvation or the primary Li + solvation sheath, whereas entropy‐driven modulation of the interfacial solvation environment by large molecular additives remains largely unexplored. Herein, fluorinated fullerene C 60 F 30 (FF) is introduced as a nanoparticle additive to create a dynamically disordered interface that enhances configurational entropy without sacrificing Li + diffusivity, while accelerating Li + desolvation and transport. Meanwhile, FF cooperates with FSI − ‐derived species to build a robust fluorine‐rich SEI, suppressing dendrite growth and parasitic reactions. As a result, Li||Li symmetric cells cycle stably for 1500 h, while high‐loading Li||LiFePO 4 cells retain 96.0% capacity after 500 cycles at 2C and 95.9% after 1000 cycles at 10C. Moreover, pouch cells and high‐loading Li||NCM811 cells further verify the practical promise of the FF‐enabled electrolyte for high‐rate, long‐cycling LMBs.
Electron-ionization-dissociation dynamics of laser-excited SO2B̃B11/ÃA21 studied using velocity map imaging
It is well known that electron-driven chemistry for electronically excited molecules is markedly different from that for their ground-state counterparts, yet in most cases, reaction mechanisms and electron scattering cross sections are determined by theory alone due to experimental challenges. We report the development of a pump–probe velocity map imaging (VMI) apparatus, where laser-excited molecules in a molecular beam subsequently interact with a dissociating electron beam. The product ions are probed using a calibrated VMI mass spectrometer to report absolute cross sections and information on the dynamics of the dissociation reactions. We demonstrate the apparatus on the electron-ionization-dissociation (EID) process of SO2 molecules excited to the electronically mixed Clements’ manifold B̃B11/ÃA21. Compared to ground-state SO2 molecules, we observed that for the state-selective EID formation of SO+ cations: (a) the thermodynamic threshold is lowered by the energy of the electronic excitation and (b) the partial cross sections with equivalent total energy are enhanced by factors of 2–4 for two distinct vibrational bands of the Clements’ manifold. Finally, the VMI images reveal that the SO+ fragments from the electronic excited states of SO2 are formed with kinetic energies up to 0.5 eV, whereas those from the ground state are predominantly below 0.2 eV. The change in the kinetic energy distribution is attributed to intramolecular vibrational relaxation and molecular geometry changes on the lower adiabatic surface of the Clements’ manifold, which shift the Franck–Condon region of the dissociative cationic state.
Accurate, sensitive, and efficient chromatin accessibility quantification at target loci using UNIChro-seq
Microbial load perturbation model identifies commensal-dependent control of cough sensitivity in health and disease
Leiomodin 2 is a processive pointed-end elongator of actin filaments
A hybrid GA–LP scenario-based framework for day-ahead scheduling of PV–BES systems with profit–robustness trade-off
Abstract This paper proposes a scenario-based scheduling framework for a photovoltaic–battery energy storage (PV–BES) system participating in day-ahead energy arbitrage markets. The proposed framework accounts for uncertainties in both PV generation and electricity prices. A hybrid optimization approach is developed, combining a genetic algorithm (GA) with a linear programming (LP) model. The optimization problem is decomposed into two layers. In the first layer, the GA determines the BES commitment schedule, while in the second layer, a coupled LP is solved to obtain the shared BES dispatch schedule, held fixed across all scenarios, with the grid exchange power varying per scenario. A robustness weight is incorporated to control the trade-off between profitability and robustness. Solving the problem across multiple values of robustness weight yields a Pareto frontier, enabling operators to select a scheduling strategy aligned with their risk preference. A case study based on real PV generation and electricity price data is conducted to validate the effectiveness of the proposed framework. The results are further compared with those obtained from three benchmark approaches: deterministic MILP, a naive rule-based method, and classical robust optimization.
Giant nonlinear Hall effect in isospin symmetry broken bilayer graphene
Abstract Spontaneous isospin ordering fundamentally reshapes quantum nonlinear transport, yet the nature of nonlinear responses in strongly correlated and symmetry-broken quantum states remain largely unexplored. In this work, we investigate a regime where symmetry breaking is not static but emerges dynamically as a tunable property of the electronic system, driven by strong correlations. Using high-quality, dual-gated Bernal bilayer graphene, we observe a giant nonlinear Hall conductivity (9.1 µm S V⁻¹) that manifests strongly in a field-driven isospin-polarized phase. In this correlated regime, the nonlinear conductivity scales exponentially with the linear conductivity, in stark contrast to the quadratic scaling expected in conventional nonlinear systems. Combined with quantum oscillation measurements and self-consistent theoretical modelling, our results indicate that this giant response is closely linked to an interaction-driven valley-polarized state. Our findings establish spontaneous isospin symmetry breaking as an effective route to giant nonlinear quantum transport, where interaction-enhanced skew scattering emerges as the dominant transport mechanism.