ACS Publications最新文献

Hydrogen is an abundant element poised to play a central role in future energy systems. When a lightweight hydrogen ion (proton, H⁺) is used as a charge carrier in Faradaic storage, it enables rapid solid-state conduction, offering strong potential for high-capacity, fast-charging electrochemical energy storage. However, the development of proton-based systems has been limited by the scarcity of suitable proton-host materials. In this study, we investigate the mechanisms of proton (de)intercalation in transition metal oxides using VO₂ polymorphs as a model system, with a focus on the role of lattice oxygen environments. Our findings reveal that protons preferentially occupy less-coordinated oxygen sites, which are energetically and structurally favorable. In addition, the presence of continuous H···O hydrogen-bonding networks facilitates solid-state proton transport via a Grotthuss-like mechanism. These insights provide a foundation for identifying and designing new proton-host materials, offering a promising strategy and design principle for advancing high-rate, high-capacity energy storage systems.

Sensitive and spatially resolved detection of intracellular microRNAs (miRNAs) is essential for understanding gene regulatory networks at the single-cell level, yet low abundance and heterogeneous distribution challenge conventional methods. Despite the availability of a variety of particle biosensors, their intracellular use for live-cell miRNA detection remains challenging. Here, we demonstrate an enabling amplification-free detection and spatial mapping of miRNAs in single cells. We employ large (∼600 nm) biocompatible microgels, which provide high local probe density, protect molecular beacons from nuclease degradation, and enhance fluorescence signals upon hybridization with target miRNAs. Microfluidic mechanoporation efficiently delivers the microgels directly into the cytosol without perturbing endogenous miRNA levels or cell viability. Functionalized microgels generate robust fluorescence signals upon hybridization with target miRNAs. In intracellular sensing, the system achieves a low-picomolar limit of detection (5.6 pM) and a dynamic range spanning three orders of magnitude (pM-nM). The biosensor also exhibits excellent specificity; negligible fluorescence was observed both with nontarget and precursor miRNAs. Application in healthy (MCF10A) and cancer (MCF7) breast cells enabled single-cell quantification of endogenous miR-191-5p and miR-363-5p, revealing variability both among individual cells and between cell types, along with distinct intracellular localization patterns reflecting multiple concentration levels. The approach combines high sensitivity, wide dynamic range, quantitative precision, and spatial resolution, allowing amplification-free monitoring of miRNA expression in live cells. This versatile platform provides a powerful tool for intracellular biosensing, with potential applications in live-cell diagnostics, therapeutic response profiling, and studies of single-cell gene regulation.

Molecular understanding of the CO₂-CH₄-H₂O mixture in clay interlayers provides crucial insights into many geochemical processes in CO₂-enchanced oil/gas recovery and CO₂ subsurface sequestrations. In this work, we developed new molecular models by optimizing the unlike-pair Lennard-Jones (LJ) parameters for the CO₂-H₂O, CH₄-H₂O and CO₂-CH₄ binary mixtures. The optimization utilizes the coupling parameter method in combination with Gibbs ensemble Monte Carlo (GEMC) simulations. The transferability of binary-derived parameters to ternary CO₂-CH₄-H₂O system is further demonstrated. These optimized parameters are used to study CO₂-CH₄-H₂O mixtures in Na-montmorillonite interlayers at 323 K and 90 bar, through grand-canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Chemical potentials of CO₂, CH₄, and H₂O in clay interlayer are calculated through the equation of state (EOS) with the Lennard-Jones referenced Statistical Associating Fluid Theory (SAFT-LJ), which is suitable for aqueous mixtures. The equilibrium basal spacing distances and species concentrations under different relative humidity (RH) and CO₂/CH₄ mole fractions are determined through extensive GCMC simulations. Importantly, using the new molecular models, we find that the trend of the sorbed CO₂ content versus the sorbed H₂O content shows good agreement with in situ infrared (IR) spectroscopy data by Loring et al. [Environmental Science& Technology, 2021, 55, 11192-11203]. While the predicted CO₂ concentrations in the monolayer hydration state (1W) is higher than the experimental results due to the heterogeneous expansion of the clay mineral in experiments, the CO₂ content in the bilayer hydration state (2W) compares remarkably well with the experimental data. The CH₄ adsorption in clay interlayers is found substantially lower than that of CO₂. In general, GCMC results show that water intercalation under high RH suppresses the sorption of CO₂ and CH₄, and that Na-montmorillonite preferentially adsorbs CO₂ over CH₄.

Gold, as a precious metal, holds irreplaceable significance in financial systems, the electronics industry, and cutting-edge technologies due to its unique physicochemical properties. To address the technical demands for gold recovery from electronic waste, we designed and synthesized ethylenedioxythiophene-functionalized conjugated organic polymers (EDOT-COPs) as Au(III) adsorbents. EDOT-COPs possess moderate porosity, thermal stability up to 350 °C, and chemical stability in acidic environments. As for the adsorption performance, EDOT-COPs achieve Au(III) uptake capacities exceeding 1700 mg g^-1 and selectively remove more than 96% of Au(III) from the mixed solutions containing eight competing metal ions such as Cu(II), Ni(II), and Pb(II). After eight consecutive adsorption-desorption cycles, EDOT-COPs still maintain high adsorption efficiency and good structural integrity. Mechanistic studies reveal that there are strong coordination bonds between EDOT groups and AuCl₄^- complexes in acidic media, along with the partial reduction of adsorbed Au(III) species. Furthermore, EDOT-COPs also demonstrate selective gold recovery from acid leachates. This work highlights the potential of functional-group-directed polymer design for developing efficient and stable adsorbents for precious metal recovery.

We assess the accuracy and limitations of the grouped-bath configuration interaction (GBCI), formerly termed the grouped-bath ansatz for the spin-flip nonorthogonal configuration interaction (SF-GNOCI), by calculating L-edge X-ray absorption spectroscopy (XAS) spectra and 2p3d resonant inelastic X-ray scattering (RIXS) spectra of transition-metal complexes. We compare the computed GBCI spectra with those from the spin-flip complete-active-space (SF-CAS) method and experiment. These comparisons demonstrate that the bath-orbital relaxation in GBCI is crucial for accurately describing both the energies and wave functions of charge-transfer states. For L-edge XAS, GBCI accounts for the core-hole relaxation neglected in SF-CAS, leading to a uniform energy shift across the spectral bands. For 2p3d RIXS, GBCI produces an energy shift in the charge-transfer band that corrects the overestimated energy in SF-CAS. Moreover, GBCI improves the wave functions of charge-transfer states, thereby correcting the RIXS intensities overestimated by SF-CAS. Nevertheless, discrepancies with experiment indicate that additional electronic correlation remains necessary. We expect that the X-ray spectral comparison presented in this study will serve as a useful benchmark for validating electronic-structure theories of transition-metal complexes.

As an emerging class of ceramic materials, high-entropy ceramics (HEC) have captured significant interest. Yet, their inherent brittleness and inelasticity restrict broader engineering applications like thermal protection. Here, we report a carboxylic ligand confinement strategy, integrating sol-gel electrospinning with optimized postcalcination treatment, enabling the scalable fabrication of flexible high-entropy (Y_0.2Yb_0.2Ho_0.2Lu_0.2Er_0.2)₃Al₅O₁₂ (RE₃Al₅O₁₂) single-crystal fiber films. We initiated the process by preparing an aluminum sol and subsequently coordinating it with carboxylate under hydrochloric acid catalysis. The inorganic colloid growth is modulated by the stoichiometric addition of tartaric acid, forming a hybrid inorganic/organic sol. Then, the sol was electrospun into precursor fiber films followed by calcination at 900 °C to form flexible RE₃Al₅O₁₂ films with a low density of 0.1398 g/cm³ and a low thermal conductivity of 25.1 mW·m^-1·K^-1. The HEC film maintains phase stability and structural integrity up to 1600 °C or in liquid nitrogen. In addition, aerogels fabricated by stacking these HEC films demonstrate an 80% strain elastic recovery and exhibit great resistance to thermal shock. This work establishes a strategy for synthesizing lightweight HEC garnet fibers poised for extreme-environment thermal protection systems.

Accurately determining protein-ligand binding free energy is critical for drug design but requires computationally expensive quantum-mechanical (QM) calculations. Fragmentation methods can mitigate this cost, yet their accuracy hinges on properly modeling the polarizing chemical environment. Here we present an application and refinement of the Electrostatically Embedded Generalized Molecular Fractionation with Conjugate Caps (EE-GMFCC) approach, termed EE-GMFCC[P-L], for computing protein-ligand interaction energies. Our method efficiently obtains the total QM energy by linearly combining the energies of capped fragments embedded in a protein point-charge field and the pairwise interactions between non-neighboring fragments. After systematically investigating methodological parameters, including ligand charge, capping scheme, and basis set, we employed the approach to calculate interaction energies for a benchmark set of 21 protein-ligand systems. The resulting data set provides a high-accuracy standard for developing and validating more approximate computational methods in structure-based drug design.

Breast cancer remains the most common cause of mortality among women globally. Although improvements in early detection and systemic therapies have enhanced patient outcomes, conventional treatment strategies, including free drug administration, are often plagued by significant limitations such as poor selectivity, systemic toxicity, rapid drug degradation, and low therapeutic indices. Paclitaxel (PTX), a commonly used chemotherapeutic drug, suffers from poor aqueous solubility and nonspecific distribution, resulting in severe off-target effects and reduced clinical efficacy. The present study investigates the potential of PTX-loaded nanoarchaeosomes (NAs) as a novel therapeutic for breast cancer rehabilitation. Paclitaxel-loaded nanoarchaeosomes (PTX-NAs) were synthesized and then characterized through various techniques, including Dynamic light scattering (DLS), Zeta (ζ) potential analysis, and Scanning Electron Microscopy (SEM). The DLS study defined the size of the PTX-NAs as ∼50 nm, with a stable surface charge of -59.8 mV. The efficiency of the loading of PTX into NAs was quantified to be about 92 ± 1%, followed by a significant 82 ± 3% PTX release within 12 h. In vitro anticancer research on MCF-7 breast cancer cells revealed a significant increase in the level of cellular death with PTX-NAs at a concentration of 0.08 μM (IC₅₀), which was 3.5-fold lower than that of free paclitaxel (0.28 μM). This indicates a significant increase in the anticancer efficacy of PTX when delivered through NAs. Biocompatibility studies on NIH 3T3 fibroblast cells confirmed that NAs alone and PTX-NAs did not induce any significant toxicity, maintaining normal cellular morphology and viability, which ensures the potential safety of this nanoformulation for clinical use. These findings suggest that PTX-NAs offer a promising, targeted approach to breast cancer therapy, providing enhanced efficacy while minimizing systemic toxicity.

The precise analysis of chiral drugs is crucial for elucidating their stereoselective pharmacological effects. As a commonly used fluoroquinolone antibiotic, ofloxacin (OFLX) exhibits different pharmacodynamics between its R- and S-OFLX, highlighting the need for efficient chiral analysis methods. This study developed a strategy based on trapped ion mobility spectrometry-mass spectrometry (TIMS-MS) and noncovalent complex formation for the rapid separation and quantification of ofloxacin enantiomers. Vancomycin and gentamicin C1a were selected as chiral selectors to form binary noncovalent complexes with the target enantiomers. TIMS analysis demonstrated that the complexes formed between R-/S-OFLX and both chiral selectors achieved baseline separation, with peak-to-peak resolution values of 1.94 and 3.34, respectively. To clarify the structural basis of chiral recognition, density functional theory calculations and the independent gradient model were employed, revealing key stereospecific weak interactions within the complexes, thereby providing critical atomic-level insight into the differential migration behavior observed in TIMS experiments at the molecular level. Based on these findings, both relative and absolute quantification methods for the enantiomers were established, both demonstrating excellent linearity and high sensitivity. Finally, the method was successfully applied to determine ofloxacin in artificial urine samples, achieving recoveries of no less than 70.60%, confirming its applicability in complex real-world matrices. This derivatization-free approach provides a robust and efficient solution for the rapid analysis of chiral drugs.

All-solution-processed perovskite optoelectronic devices are promising for scalable, sustainable manufacturing, yet their performance remains inferior to vacuum-deposited counterparts because solvents used for subsequent charge transport layers often damage the underlying emissive layer. Herein, we find that when fabricating the electron transport layer (ETL) on sky-blue quasi-2D perovskite films using solution processing, even nonpolar solvents degrade luminescence properties and surface morphology, primarily due to the loss of organic ligands and additives. To overcome this challenge, we develop a supramolecular host-guest complexation strategy that predissolves these organic components in nonpolar solvents and incorporates them directly into the ETL processing sequence. Using this method, we achieve a sky-blue PeLED with an external quantum efficiency of 14.75% and a maximum luminance of 8740 cd m^-2. This work provides a versatile and promising route to high-performance, all-solution-processed PeLEDs.