化学•材料最新文献

Triplet photosensitizers are essential in photocatalytic hydrogen production and photoredox organic transformations, relying on efficient light absorption, intersystem crossing, and subsequent electron or energy transfer processes. Recent developments have focused on transition metal complexes with favorable electronic configurations, such as Cu(I) complexes, which feature extended excited-state lifetimes and reduced nonradiative decay. In contrast, Zn(II) complexes, despite being isoelectronic with Cu(I), are generally dismissed as photosensitizers because they predominantly exhibit ligand-centered emission, and MLCT states, when observed, are short-lived and poorly suited for photocatalysis. Nonetheless, their tunable coordination chemistry, low toxicity, and catalytic potential make them promising candidates. In this work, we demonstrate that Zn(II) complexes can be deliberately engineered to act as efficient triplet photosensitizers by exploiting intraligand charge transfer (ILCT) rather than MLCT. We report a comparative study of Zn(II) complexes supported by redox-noninnocent tridentate pincer ligands bearing different aryl substituents, revealing pronounced differences in triplet-state behavior. Structural analysis shows that coplanarity between the aryl-azo and phenanthroline moieties is essential for efficient ILCT and long-lived triplet emission. To elucidate the role of the metal center, a structurally analogous Cd(II) complex was examined, which exhibits photophysical behavior nearly identical to its Zn(II) counterpart, confirming that the metal primarily enforces ligand geometry rather than participating electronically in the excited state. Both Zn(II) and Cd(II) complexes function as effective photosensitizers for singlet-oxygen-mediated oxidation, achieving photocatalytic efficiencies of approximately 50%. Although this efficiency is lower than that of certain Ir-based systems, this work establishes a design strategy in which unfavorable metal-centered electronic interactions are intentionally bypassed, and the metal serves chiefly as a structural anchor. These findings position Zn(II) complexes as sustainable, earth-abundant photosensitizers and provide a new framework for designing triplet photosensitizers based on closed-shell metal ions.

Ether-based electrolytes have gained increasing attention for energy storage based on their utility as solvate ionic liquids at high concentration and their role in forming effective cointercalation complexes at graphite electrodes. While transferrable atomistic models have been proposed to describe glyme ether solutions at varying concentration and backbone chain lengths, coarse-grained models have not been extensively explored. The need for coarse-grained descriptions is emphasized by the formation of potentially mesoscale aggregate structures which enable efficient ion transport. Herein we describe a simple approach to developing such models using a combination of a charge smearing for long-ranged electrostatics and Boltzmann Inversion to develop short-ranged tabulated potentials. The impact of long-ranged interactions on electrolyte structure and the ingredients to the coarse-grained models are discussed along with the importance of system selection for training the short-ranged portion. Overall, the final model shows good transferability for diglyme and monoglyme, which share an emphasis on ion association, but fails to capture the solvent separated ionic structure of triglyme electrolytes.

Coastal salt marshes (CSMs) are vital blue carbon (BC) reservoirs, yet accurately quantifying their gross primary productivity (GPP) remains challenging due to limitations in terrestrial biosphere models (TBMs), which often overlook coastal-specific processes. Here, we present SAL-GPP, a process-based model that incorporates coastal-specific modules to capture the effects of salinity and temperature stress on photosynthesis, as well as light-use efficiency across salinity gradients in diverse CSM plant species. Model validation showed strong agreement with observations, with R² of 0.82 and model efficiencies of 0.82 and 0.74 for daily and seasonal GPP, respectively. Driven with global inputs, SAL-GPP produced high-resolution global simulations, yielding a mean annual GPP of 66.89 ± 11.68 TgC yr^-1 (2011-2020), with 64% concentrated in key hotspots across the southeastern United States, western Europe, southeastern China, and Australia. From 2011 to 2016, global CSM GPP increased by 1.56 TgC yr^-1, then declined, rebounded after 2018, and peaked at 71.45 ± 12.02 TgC yr^-1 in 2020. Model evaluation showed that SAL-GPP outperformed existing remote sensing-based GPP products and TBMs at both site and grid levels. By explicitly incorporating coastal ecosystem dynamics, SAL-GPP supports global BC accounting and climate mitigation strategies aligned with nature-based solutions for carbon neutrality.

Whether used as an alternative fuel or a clean feedstock, renewable hydrogen (H₂) could facilitate the deep decarbonization of hard-to-abate sectors, which is essential to meet China's carbon neutrality target. Nevertheless, the nationwide H₂ backbone networks required have not yet been fully investigated. Employing a techno-economic analysis of solar photovoltaic and wind power on a scale of 1 km combined with source-sink matching among potential multisectoral H₂ hubs, this study develops a decision support system (dubbed China Shared Hydrogen Infrastructure Network Enabler (SHINE)) to explore renewable H₂ layouts commensurate with China's climate ambition, accounting for varying degrees of H₂ demand and reuse of oil and gas pipeline corridors. Given total H₂ demand scenarios of 54, 77, and 100 Mt/yr in 2060, the total length of the proposed trunkline networks will reach roughly 11,700, 18,300, and 29,900 km, with a levelized cost of production and transport of 1.55, 1.62, and 1.72 USD/kg, respectively. Additionally, by incorporating the spatial heterogeneities and sectoral disparities of H₂ deployment expansion into the model, distinct policy instruments can be crafted for the shared nationwide H₂ network.

Antibody-drug conjugates (ADCs) are modern biopharmaceuticals that combine the therapeutic effects of small-molecule drugs with the outstanding selectivity of monoclonal antibodies (mAbs). Since their introduction in the biomedical field, research has focused on elucidating the structure, stability, and mode of action of ADCs. Nevertheless, standard characterization methods for ADCs heavily rely on disruptive techniques like mass spectrometry in a non-physiological environment. Here, we present an NMR approach combining ¹H-¹³C ALSOFAST-HMQC and T₂-edited ¹H CPMG experiments, which together provide information on: i. the fingerprint and higher-ordered structure (HOS) of mAbs and ADCs and ii. the properties of the bound linker-payload fragment. In this study, we chose Trastuzumab as a well-known mAb and a Remdesivir-derived fragment as a linker-payload model system to validate our approach.

Post-translational modifications (PTMs) such as phosphorylation, acetylation, and methylation critically expand proteome function by regulating protein structure and interactions. Hydropathy changes serve as a main driving force; however, a quantitative, mechanistic understanding of how their distinct chemical changes alter local protein hydropathy remains limited. To bridge this gap, we extend the Protocol for Assigning a Residue's Character on a Hydropathy (PARCH) scale, a residue-level hydropathy scale, to systematically evaluate PTM-induced physicochemical changes. By applying this method, we quantify the effect and magnitude of hydropathy shifts at modification sites and map how these perturbations influence the local protein environment. Our analysis reveals that phosphorylation exerts a strong, consistent hydrophilic effect, significantly increasing PARCH values due to the introduction of a large, charged phosphate group. In contrast, N-lysine acetylation, which neutralizes charge, shows context-dependent effects, predominantly increasing the hydrophobicity but occasionally enhancing the local hydrophilicity. Methylation presents the most complex signature, with no uniform trend, where increased side chain bulk can paradoxically increase water exposure despite the modification's nonpolar nature. This study establishes the PARCH scale as a powerful quantitative tool for deciphering how PTMs regulate the local hydropathy landscape of proteins, providing a predictive foundation for understanding their structural, hydropathy, and functional consequences.