化学•材料最新文献

Currently, there is no effective treatment for glioblastoma multiforme (GBM), the most frequent and malignant type of brain tumor. The blood-brain (tumor) barrier (BB(T)B), which is composed of tightly connected endothelial cells and pericytes (with partial vasculature collapse), hampers nanomedicine accumulation in tumor tissues. We aimed to explore the effect of nanomedicine size on passive targeting of GBM. A series of size-tunable poly(ethylene glycol) (PEG)-grafted copolymers (gPEGs) were constructed with hydrodynamic diameters of 8-30 nm. Biodistribution studies using orthotopic brain tumor-bearing mice revealed that gPEG brain tumor accumulation was maximized at 10 nm with ∼14 dose %/g of tumor, which was 19 times higher than that in the normal brain region and 4.2 times higher than that of 30-nm gPEG. Notably, 10-nm gPEG exhibited substantially higher brain tumor accumulation than 11-nm linear PEG owing to the prolonged blood circulation property of gPEGs, which is derived from a densely PEG-packed structure. 10 nm gPEG exhibited deeper penetration into the brain tumor tissue than the larger gPEGs did (>10 nm). This study demonstrates, for the first time, the great potential of a nanomedicine downsizing strategy for passive GBM targeting.

The redox properties of the actinides in aqueous solution are important for fuel production/reprocessing and understanding the environmental impact of nuclear waste. The redox potentials for U, Np, Pu, and Am in oxidation states from 0 up to VII (as appropriate) in aqueous solutions have been predicted at the density functional theory level with the B3LYP functional, Stuttgart small core pseudopotential basis sets for the actinides, and explicit (30H₂O molecules)/implicit treatment of the aqueous solvent using the self-consistent reaction field COSMO and SMD approaches for the implicit solvation. The predictions of the structural parameters of clusters incorporating first and second solvation shells are consistent with the available experimental data. Our results are typically within 0.2 V of the available experimental data using two explicit solvation shells with an implicit solvent model. The use of the PW91 functional substantially improved the prediction of the Pu(VI/V) redox couple. The redox couples for An(VI/IV) and An(V/IV) which involve the addition of protons and removal of the actinyl oxygens led to slightly larger differences from an experiment. The An(IV/0) and An(III/0) couples were reliably predicted with our approach. Predictions of the unknown An(II/I) redox potentials were negative, consistent with expectations, and predictions for unknown An(VII/VI), An(III/II), and An(II/0) redox couples improve prior estimates.

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO₂-based supports through H₂ reduction pretreatment. The Pt catalysts supported by defective CeO₂-based supports, including CeO₂, CeZrO_x, and CeO₂/Al₂O₃ (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (Pt_C) with the bottom layer of Pt atoms substituting the Ce cations in the CeO₂ surface lattice can be obtained through reduction activation. Embedded Pt_C can better facilitate CO adsorption and promote O₂ activation at Pt_C-CeO₂ interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.

Monitoring of volatile organic compounds (VOCs) in air is crucial for understanding their atmospheric impacts and advancing their emission reduction plans. This study presents an innovative integrated methodology suitable for achieving semireal-time high spatiotemporal resolution three-dimensional measurements of VOCs from ground to hundreds of meters above ground. The methodology integrates an active AirCore sampler, custom-designed for deployment from unmanned aerial vehicles (UAV), a proton-transfer-reaction mass spectrometry (PTR-MS) for sample analysis, and a data deconvolution algorithm for improved time resolution for measurements of multiple VOCs in air. The application of the deconvolution technique significantly improves the signal strength of data from PTR-MS analysis of AirCore samples and enhances their temporal resolution by 4 to 8 times to 4-11 s. A case study demonstrates that the methodology can achieve sample collection and analysis of VOCs within 45 min, resulting in >120-360 spatially resolved data points for each VOC measured and achieving a horizontal resolution of 20-55 m at a UAV flight speed of 5 m/s and a vertical resolution of 5 m. This methodology presents new possibilities for acquiring 3-dimensional spatial distributions of VOC concentrations, effectively tackling the longstanding challenge of characterizing three-dimensional VOC distributions in the lowest portion of the atmospheric boundary layer.

Fabrication of robust isolated atom catalysts has been a research hotspot in the environment catalysis field for the removal of various contaminants, but there are still challenges in improving the reactivity and stability. Herein, through facile doping alkali metals in Pt catalyst on zirconia (Pt-Na/ZrO₂), the atomically dispersed Pt^δ+-O(OH)_x- associated with alkali metal via oxygen bridge was successfully fabricated. This novel catalyst presented remarkably higher CO and hydrocarbon (HCs: C₃H₈, C₇H₈, C₃H₆, and CH₄) oxidation activity than its counterpart (Pt/ZrO₂). Systematically direct and solid evidence from experiments and density functional theory calculations demonstrated that the fabricated electron-rich Pt^δ+-O(OH)_x- related to Na species rather than the original Pt^δ+-O(OH)_x-, serving as the catalytically active species, can readily react with CO adsorbed on Pt^δ+ to produce CO₂ with significantly decreasing energy barrier in the rate-determining step from 1.97 to 0.93 eV. Additionally, owing to the strongly adsorbed and activated water by Na species, those fabricated single-site Pt^δ+-O(OH)_x- linked by Na species could be easily regenerated during the oxidation reaction, thus considerably boosting its oxidation reactivity and durability. Such facile construction of the alkali ion-linked active hydroxyl group was also realized by Li and K modification which could guide to the design of efficient catalysts for the removal of CO and HCs from industrial exhaust.

With the annual global electricity production exceeding 30,000 TWh, the safe transmission of electric power has been heavily relying on SF₆, the most potent industrial greenhouse gas. While promising SF₆ alternatives have been proposed, their compatibilities with materials used in gas-insulated equipment (GIE) must be thoroughly studied. This is particularly true as the emerging SF₆ alternatives generally leverage their relatively higher reactivity to achieve lower global warming potentials (GWPs). Here, a high-throughput compatibility screening of common GIE materials was conducted with a representative SF₆ alternative, namely, C₄F₇N (2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile)/CO₂ gas mixtures. In this screening, the insulation performance of C₄F₇N/CO₂ gas mixtures, as an indicator of the C₄F₇N/materials compatibility level, was periodically monitored during the thermal aging with tens of materials from SF₆-insulated GIE, including desiccants/adsorbents, rubber, plastics, composites, ceramics, metals, etc. The identification of incompatible materials and the follow-up mechanism studies suggested that the acidity of materials represents the primary cause for C₄F₇N/materials incompatibility when C₄F₇N/CO₂ gas mixtures are used as a drop-in replacement solution for existing SF₆-insulated apparatuses. Mitigation strategies tackling the acidity of materials were then proposed and validated. Additionally, the amphoteric characteristics of C₄F₇N were briefly discussed. This work provides insight into the materials incompatibility of SF₆ alternatives, along with validated mitigation strategies, for the selection and design of materials used in future eco-friendly GIE.

As the number of coastal nuclear facilities rapidly increases and the wastewater from the Fukushima Nuclear Plant has been discharged into the Pacific Ocean, the nuclear environmental safety of China's marginal seas is gaining increased attention along with the heightened potential risk of nuclear accidents. However, insufficient work limits our understanding of the impact of human nuclear activities on the Yellow Sea (YS) and the assessment of their environmental process. This study first reports the ¹²⁹I and ¹²⁷I records of posthuman nuclear activities in the two YS sediments. Source identification of anthropogenic ¹²⁹I reveals that, in addition to the gaseous ¹²⁹I release and re-emission of oceanic ¹²⁹I discharged from the European Nuclear Fuel Reprocessing Plants (NFRPs), the Chinese nuclear weapons testing fallout along with the global fallout is an additional ¹²⁹I input for the continental shelf of the YS. The ¹²⁹I/¹²⁷I atomic ratios in the North YS (NYS) sediment are significantly higher than those in the other adjacent coastal areas, attributed to the significant riverine input of particulate ¹²⁹I by the Yellow River. Furthermore, we found a remarkable ¹²⁹I latitudinal disparity in the sediments than those in the seawaters in the various China seas, revealing that sediments in China's marginal seas already received a huge anthropogenic ¹²⁹I from terrigenous sources via rivers and thus became a significant sink of anthropogenic ¹²⁹I. This study broadens an insight into the potential impacts of terrigenous anthropogenic pollution on the Chinese coastal marine radioactive ecosystem.

Dissolved organic matter (DOM) in aquatic systems is a highly heterogeneous mixture of water-soluble organic compounds, acting as a major carbon reservoir driving biogeochemical cycles. Understanding DOM molecular composition is thus of vital interest for the health assessment of aquatic ecosystems, yet its characterization poses challenges due to its complex and dynamic chemical profile. Here, we performed a comprehensive chemical analysis of DOM from highly urbanized river and seawater sources and compared it to drinking water. Extensive analyses by nontargeted direct infusion (DI) and liquid chromatography (LC) high-resolution mass spectrometry (HRMS) through Orbitrap were integrated with novel computational workflows to allow molecular- and structural-level characterization of DOM. Across all water samples, over 7000 molecular formulas were calculated using both methods (∼4200 in DI and ∼3600 in LC). While the DI approach was limited to molecular formula calculation, the downstream data processing of MS2 spectral information combining library matching and in silico predictions enabled a comprehensive structural-level characterization of 16% of the molecular space detected by LC-HRMS across all water samples. Both analytical methods proved complementary, covering a broad chemical space that includes more highly polar compounds with DI and more less polar ones with LC. The innovative integration of diverse analytical techniques and computational workflow introduces a robust and largely available framework in the field, providing a widely applicable approach that significantly contributes to understanding the complex molecular composition of DOM.

Of late, siloxane-containing vitrimers have gained significant interest due to their fast dynamic characteristics over a reasonable temperature range (180-220 °C), making them well-suited for diverse applications. The exchange reaction pathway in the siloxane vitrimers is accountable for the covalent adaptive network, with the reaction's effectiveness being regulated by either organic or organometallic catalysts. However, directly studying the exchange reaction pathway in the bulk phase using experimental approaches is challenging because of the intricate and interconnected structure of these vitrimers. Here, we perform comprehensive density functional theory (DFT) and experimental investigations to discover the detailed catalytic efficacy of siloxane exchange and provide direction for the reaction process using a 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyst. The calculated transition barrier energy and catalytic efficiency of hexamethyldisiloxane and dihydroxy-dimethylsilane exchange derived from the nudged elastic band with transition-state calculations strongly agree with the experimental findings. In addition, Fukui indices, along with partial charges, are employed to evaluate the nucleophilic and electrophilic behaviors of silanol and siloxane molecules. Our analysis revealed that by utilizing the Fukui indices of both the acid and the base, we can make an approximate estimation of the respective kinetics of the S_N2 process in the siloxane exchange reaction mechanism. These findings establish a foundation for comprehending a crucial aspect of the exchange mechanism in siloxane vitrimer systems and could aid in the development of novel catalysts.

Mechanofluorochromic materials are a type of "smart" material because of their adjustable fluorescent properties under external mechanical force, making them significant members of the materials family. However, as the fluorescent characteristics of these materials highly depend on their microstructures, the still insufficiently in-depth research linking molecular structures to light emission motivates researchers to explore the fluorescent properties of these materials under external stimuli. In this work, based on synthetic [AgS₄] microplates, we explore a fascinating mechanical-induced photoluminescent enhancement phenomenon. By applying mechanical force to solid-state [AgS₄] to damage the surface morphology, a significant enhancement in photoluminescence is observed. Moreover, the emitted intensity increases with the extent of damage, which can be attributed to alterations in crystallinity. This work provides valuable insights into the relationship among photoluminescence, crystallinity, and mechanical force, offering new strategies for designing luminescent devices.