ACS Earth and Space Chemistry最新文献

The precise control of the assembly structure and size of gold nanoclusters (AuNCs) can potentially amplify their near-infrared II (NIR-II) fluorescence imaging and targeting properties. However, the conventional electrostatic assembly of AuNCs and charged molecules faces challenges in balancing the inherent electrostatic repulsions among charged units and regulating the diffusion of assembly units. These difficulties limit precise control over assembly size and structure, along with limited options for coassembled molecules, thereby restricting imaging properties and targeting capability. To circumvent this challenge, we developed a reverse emulsion-confined electrostatic assembly method. This technique efficiently constructs AuNC nanoassemblies with diverse coassembled molecules, allowing for the fine-tuning of assembly size and structure, including both core-satellite and homogeneous AuNC nanoassemblies. The development of two distinct nanoassemblies can be partially attributed to the varying diffusive rates of AuNCs or the AuNCs/polymer complex within the fused emulsion droplets. This variance arises from steric hindrances encountered during the emulsion fusion process. Interestingly, core-satellite nanoassemblies exhibit the strongest NIR-II fluorescence enhancement. Finally, the introduction of a hyaluronic acid coating on the surfaces of nanoassemblies with varying sizes enables the nanoprobes to achieve enhanced lymph node imaging through size modulation and macrophage targeting, which are used for surgical navigation to remove lymph node metastases. We envision that this self-assembly strategy can be extended to a wide range of electrostatic assembly systems for the development of multicomponent functional materials.

Hybrid organic-inorganic perovskites play a critical role in modern optoelectronic applications, particularly as single photon sources due to their unusual bright ground state. However, the presence of trap states resulting from surface dangling bonds hinders their widespread commercial application. This work uses density functional theory (DFT) to study the effects of various passivating ligands and their binding sites on Rashba splitting, a phenomenon directly linked to the bright ground state. Our results predict that X2- and X4-type ligands that adsorb at acidic oxygen binding sites and zwitterionic binding sites efficiently eliminate trap states introduced by surface iodine vacancies. Furthermore, our results show that distortions from the nominally symmetric cubic structure of the perovskite predominantly determine the presence and magnitude of the Rashba splitting. Specifically, the loss of more symmetry elements consistently leads to Rashba splitting in both the valence band (VB) and the conduction band (CB) with small Rashba splitting coefficients. Conversely, although inversion symmetry breaking alone fails to guarantee the presence of pure Rashba splitting in both the VB and the CB, it significantly increases the degree of splitting. The adsorption of ligands not only mitigates trap states but also plays a critical role in altering the local symmetry, thus influencing Rashba splitting. DFT predicts a distinct Rashba-Dresselhaus splitting in the CB with X2 ligands, causing the largest splitting. The presence of local electric fields causes consistent Rashba splitting of the VB across all studied systems except for the X4 zwitterionic passivated systems (sulfobetaine and lecithin). Electric fields are predicted to cause significant splitting of the CB, particularly for MAPbI₃ and SH passivated MAPbI₃ surfaces that possess freely rotating ligand binding sites. This study reveals that the wavelength, tunability of Rashba splitting through an applied electric field, and nature of Rashba-Dresselhaus splitting are influenced by the characteristics of the ligand binding site. On the other hand, pure Rashba splitting is predicted to exhibit a greater susceptibility to symmetry distortion than to specific ligand binding sites. These findings elucidate how surface passivating ligands and symmetry distortions influence Rashba splitting, shaping the optoelectronic properties of perovskite nanocrystals.

Maintaining the surface structure stability of LiCoO₂ (LCO) during rapid charge-discharge processes (>5C) and under high-voltage conditions (>4.2 V) is challenging due to interfacial side reactions, cobalt dissolution, and oxygen redox activity at deeply delithiated states, all of which contribute to performance degradation. Herein, different from traditional surface coating methods, we report a water-mediated strategy that modifies the surface architecture of LCO, creating a passivating layer to inhibit surface degradation and enhance cycling stability under fast charging conditions. The surface etching of LCO by H₂O is accompanied by a concurrent Li⁺/H⁺ cation exchange, which passivates surface oxygen with H⁺ ions, thereby enhancing both the hydrophobicity and structural stability. Consequently, the modified LCO exhibits superior capacity retention, which is 2.5 times that of the pristine LCO, after 100 cycles at a current density of 1000 mA g^-1 (∼6C at 4.5 V). Even at an elevated temperature of 45 °C, it maintains impressive cycling stability at a current density of 500 mA g^-1 (∼3C), as demonstrated in practical full-cell configurations. Investigation with multiple samples confirmed that the water-mediated strategy demonstrated broad applicability. We emphasize that the water-mediated modification of the surface architecture on cathode materials offers significant insights into enhancing the stability of high-energy-density lithium-ion batteries (LIBs).

Laser-induced graphene (LIG) has attracted considerable attention for its use in flexible and stretchable sensors, owing to its electrical/mechanical properties and scalable fabrication processes. Although laser scanning facilitates the formation of LIG and its strain sensor, the strain-sensing sensitivity enhancement of LIG remains limited by the material's properties and structural design. In this study, we demonstrate a substantial improvement in sensitivity that was achieved by fabricating a LIG using ZnO nanoparticle (NP)-assisted photothermal enhancement. The results show that ZnO NPs selectively reduce the threshold fluence needed to convert polyimide (PI) into LIG. By transferring the LIG formed on PI to poly(dimethylsiloxane), we fabricate a stretchable strain sensor with ultrahigh sensitivity and a gauge factor of 1214 at 10% strain, which is approximately 60 times higher than the gauge factor without ZnO NPs. Using the selective graphenization properties of LIG, a flexible, dual-sided integrated sensor sheet that is equipped with flexible strain and ultraviolet (UV) sensors is demonstrated. This sheet enables simultaneous monitoring of UV intensity and joint bending angles of sports wearable devices. We validated the developed sensors by attaching them to a runner's body to monitor and simulate forefoot and heel strikes, demonstrating the sensor's ultrahigh sensitivity and long-term stability without the need for a camera. These findings highlight the potential of the proposed method for developing multifunctional sensor applications with ultrahigh sensitivity and stability.

Group A rotaviruses (RVA) remain one of the dominant pathogens causing diarrhea in children under 5 years of age worldwide, despite a sharp decrease of RVA-associated diarrhea and mortality since the introduction of rotavirus vaccines. The decreased effectiveness of live attenuated rotavirus vaccines, coupled with the emergence of new rotavirus genotypes and the risk of cross-species virus transmission, underscores the necessity to develop more effective and broad-spectrum rotavirus vaccines. In this study, we utilized nanoparticles coupled with the SpyCatcher-SpyTag system to effectively display the truncated VP8-1 protein. The modular display of the monovalent VP8-1 proteins markedly increased the immunogenicity of VP8-1. Furthermore, the bivalent display of VP8-1 proteins from simian rotavirus SA11 and lamb rotavirus LLR on the same particle not only increased immunogenicity against homotypic antigens but also elicited robust heterotypic immune responses and conferred effective protection against a distant heterotypic rotavirus with sequence identities of only 62%-66% in an adult mouse model. Therefore, mosaic VP8 nanoparticles could be considered as a viable strategy for the development of the next-generation broad-spectrum rotavirus vaccine.

Cavity-enhanced emission of electrically controlled semiconductor quantum dots (QDs) is essential in the development of bright quantum devices for real-world quantum photonic applications. Combining the circular Bragg grating (CBG) approach with a PIN-diode structure, we propose and implement designs for ridge-based electrically contacted QD-CBG resonators. Through fine-tuning of device parameters in numerical simulations and deterministic nanoprocessing, we produced electrically controlled single QD-CBG resonators with excellent electro-optical emission properties. These include multiple wavelength-tunable emission lines and a photon extraction efficiency (PEE) of up to 30.4(3.4)%, where refined numerical optimization based on experimental findings suggests a substantial improvement, promising PEE > 50%. Additionally, the developed quantum light sources yield single-photon purity reaching 99.2(2)% and photon indistinguishability of 75(5)% under quasi-resonant p-shell excitation. Our results present high-performance quantum devices with combined cavity enhancement and deterministic charge-environment controls, which are relevant for the development of photonic quantum information systems such as complex quantum repeater networks.

Developing conductive electrocatalysts is crucial for decreasing the ohmic loss induced by electric resistance of the catalyst layer in the large-current-density hydrogen evolution reaction (HER), which has been overlooked previously. In this study, we screen a highly conductive antiperovskite CdNNi₃ with negligible ohmic loss, as a highly active and durable HER electrocatalyst capable of unlocking ampere-scale current densities. CdNNi₃ exhibits an impressive activity (an overpotential of 235 mV) at 1 A cm^-2 and maintains its performance steadily at an ampere-scale current density (at 1 A cm^-2 over 400 h). Besides, the CdNNi₃-enabled anion-exchange membrane water electrolyzer outperforms that of the benchmark Pt/C, evidenced by a reduced cell voltage of 160 mV at 1 A cm^-2, and presents a favorable stability at 1 A cm^-2. Importantly, this study experimentally discovers the dynamic surface reconstruction phenomena of antiperovskite nitrides during alkaline HER. Theoretical analysis suggests that the presence of Cd in the reconstructed surface effectively adjusts the local electronic configuration of active sites, which promotes the adsorption of OH and reduces the binding strength to H, thereby facilitating the water dissociation step and reducing the energy barrier of the potential-determining step in the HER process.

Bacterial pneumonia is one of the most challenging global infectious diseases with high morbidity and mortality. Considering the antibiotic abuse and resistance of bacterial biofilms, a variety of metal-based materials have been developed. However, due to the high oxygen environment of the lungs, some aerobic infection bacteria have high tolerance to oxygen and ROS, and most of the metal-based materials based on ROS may not achieve good therapeutic effects. Inspired by the sensitivity of cuproptosis to aerobic respiratory cells, we designed a copper composite antibacterial nanoparticle and found that it can effectively induce cuproptosis-like death in the aerobic bacteria of the lungs. To address the challenge of in vivo application of cuproptosis, manganese dioxide was first incorporated to deplete protective glutathione, which can interact with copper and thus hinder the interaction of copper with proteins and assist in antibacterial action through immune enhancement. Cuproptosis-like death also requires a large number of copper ions. To meet this demand, we deliver positively hydrophilic modified composite nanoparticles that effectively penetrate the lung mucus layer directly to the lungs through local administration, and the copper ions are further released rapidly by the acidic environment at the infected site, which can further destroy bacterial biofilms in synergy with manganese. This drug-delivery system can effectively treat pneumonia caused by aerobic bacteria and avoid systemic toxicity that can be caused by large doses of copper.

Circularly polarized luminescent (CPL) materials have garnered considerable interest for a variety of advanced optical applications including 3D imaging, data encryption, and asymmetric catalysis. However, the development of high-performance CPL has been hindered by the absence of simple synthetic methods for chiral luminescent emitters that exhibit both high quantum yields and dissymmetry factors. In this study, we present an innovative approach for the synthesis of macro-chiral liquid crystal quantum dots (Ch-QDs/LC) and their CPL performance enhancement through doping with 4-cyano-4'-pentylbiphenyl (5CB), thus yielding a CPL-emitting generator (CEG). The Ch-QDs/LCs were synthesized, and their surfaces functionalized with a chiral mesogenic ligand, specifically cholesteryl benzoate, anchored via a lipoic acid linker. Under the regulation of chiral 2S-Zn²⁺ coordination complexes, the chiral LC encapsulation process promotes coordinated ligand substitution, resulting in an exceptional quantum yield of 56.3%. This is accompanied by high absorption dissymmetry factor (g_abs) and luminescence dissymmetry factor (g_lum) values ranging from 10^-3 to 10^-2, surpassing most reported dissymmetry factors by at least an order of magnitude. The modular Ch-QDs/LCs demonstrate the ability to transfer chirality to the surrounding medium efficiently and manifest macro-chiral characteristics within a nematic LC matrix. Utilizing Ch-QDs/LC as an effective CPL emitter within achiral 5CB matrices enabled the system to achieve a maximum g_lum value of 0.35. The resultant CEG device acted as a direct CPL source, initiating enantioselective photopolymerization.