Abstract Spatiotemporal manipulation of biological processes in living animals using noninvasive, remote-controlled stimuli is a captivating but challenging endeavor. Herein, we present the development of a biocompatible photocatalytic technology termed CAT-NIR, which uses external near infrared light (NIR, 740?nm) to trigger decaging reactions in living mice. The Os(II) terpyridine complex was identified as an efficient NIR photocatalyst for promoting deboronative hydroxylation reactions via superoxide generation in the presence of NIR light, resulting in the deprotection of phenol groups and the release of bioactive molecules under living conditions. The validation of the CAT-NIR system was demonstrated through the NIR-triggered rescue of fluorophores, prodrugs as well as biomolecules ranging from amino acids, peptides to proteins. Furthermore, by combining genetic code expansion and computer-aided screening, CAT-NIR could regulate affibody binding to the cell surface receptor HER2, providing a selective cell tagging technology through external NIR light. In particular, the tissue-penetrating ability of NIR light allowed for facile prodrug activation in living mice, enabling noninvasive, remote-controlled rescue of drug molecules. Given its broad adaptability, this CAT-NIR system may open new opportunities for manipulating the functions of bioactive molecules in living animals using external NIR light with spatiotemporal resolution.
The porous defective MIL-88B(Fe) with abundant oxygen vacancies and Fe-N sites was fabricated to accomplish nearly zero peroxydisulfate (PDS) consumption for persistent bisphenol A (BPA) degradation via electron-transfer pathway (ETP). Interestingly, the generated sulfates during ETP were oxidized to yield the confined sulfate radicals and to accomplish the peroxydisulfate regeneration in the fine-tuned MIL-88B(Fe), which was verified by series experiments and DFT calculations. Further studies suggested that the optimal De-MIL-88B(Fe)-1.25 catalyst achieved the persistent nonradical reactions for BPA decomposition under visible light irradiation with both low input and low consumption of PDS. It was the first case to achieve nearly zero PDS consumption for emerging pollutants elimination, which provided new strategy to design and tune defective metal-organic frameworks for the purpose of reducing the stoichiometry between PDS and contaminants for nearly zero PDS consumption.
Given the deficiencies of traditional government capacity indicators and cultural factors (e.g., individualism) in explaining the discrepancies of different agents' responses to the coronavirus disease 2019 (COVID-19) pandemic, the present study proposed and examined the role of neoliberalism, a novel cultural tradition of knowledge emphasizing the principles of free markets and self-governance, as an additional explanation of the discrepancies in the governmental and individual responses to the pandemic. Analyzing policy responses of 106 nations and personal responses from 105,203 individuals in 104 nations during the first wave of the pandemic, we found that nation-level neoliberalism (delineated by the economic freedom index) negatively predicted the nonlinear trajectories of government policy responses to contain the pandemic. Specifically, in more neoliberal countries, stringent containment policy responses showed a sharper decline in the later stage of the first wave of the pandemic. Moreover, nation-level neoliberalism negatively predicted individuals' pandemic-protective attitudes and behaviors. All these effects are independent of and incremental to those of nation-level individualism. In conclusion, this study sheds light on how neoliberalism could lead to negative consequences during large-scale, long-lasting public threats, offering practical guidance for adjusting public crisis management in the future.
Abstract Aim Quantifying niche shifts of non-native species and their interactions with natives is vital in evaluating invasion risk yet remains difficult. Climate filtering and competition with native congeners are two important processes impacting niche changes and yielding contradictory predictions for the coexistence of non-native and native species. Closely related species representing the Eastern Asia (EA)?Eastern North America (ENA) floristic disjunction provide a powerful yet unexplored system for assessing the relative roles of these two processes. Here, we tested three niche change scenarios (unfilling, expansion and stable) using EA species naturalized in ENA. We aim to answer: (1) which scenario is observed for naturalized species? and (2) how has niche overlap between EA and ENA congeners changed after naturalization? Location ENA and EA. Time Period Present. Major Taxa Studied Angiosperms. Methods Niches were estimated using both occurrences and predictions generated by ecological niche models. Niche changes of naturalized species and their niche overlap with natives were measured using Schoener's D. Contributions of niche expansion and unfilling on niche changes of naturalized niches were evaluated using hierarchical partitioning and linear regressions. We further measured pairwise phylogenetic distances among EA and ENA congeners and evaluated the association with niche overlap. Results Unfilling-dominated postintroduction niche changes of the naturalized species. EA species naturalized in ENA exhibited lower niche overlap with ENA native congeners compared with native range populations in EA. These results remain when considering time since introduction and potential physical dispersal limitations interpreted by projecting suitable niche space between EA and ENA. However, dispersal limitation may contribute to the degree of niche unfilling. Main Conclusions Using intercontinental disjunct species as a study system, we found that naturalization is shaped jointly by climate filtering and competition with native congeners, providing valuable insights for evaluating invasion risk underlying global floristic exchanges.
An approach to generalize any kind of collinear functional in density functional theory to noncollinear functionals is proposed. This approach satisfies the correct collinear limit for any kind of functional, guaranteeing that the exact collinear functional after generalization is still exact for collinear spins. Besides, it has well-defined and numerically stable functional derivatives, a desired feature for noncollinear and spin-flip time-dependent density functional theory. Furthermore, it provides local torque, hinting at its applications in spin dynamics.
Nonlocal modeling has drawn more and more attention and becomes steadily more powerful in scientific computing. In this paper, we demonstrate the superiority of a first-principle nonlocal model—Wigner function—in treating singular potentials which are often used to model the interaction between point charges in quantum science. The nonlocal nature of the Wigner equation is fully exploited to convert the singular potential into the Wigner kernel with weak or even no singularity, and thus highly accurate numerical approximations are achievable, which are hardly designed when the singular potential is taken into account in the local Schrödinger equation. The Dirac delta function, the logarithmic, and the inverse power potentials are considered. Numerically converged Wigner functions under all these singular potentials are obtained with a fourth-order accurate operator splitting spectral method, and display many interesting quantum behaviors as well.
In this work, an excitonic energy transfer (EET) based non-radical mechanism was proposed for the degradation of organic pharmaceuticals by graphitic carbon nitride (g-C3N4) under visible light irradiation. Using diclofenac (DCF) as a model molecule, the competition between single electron transfer (SET) and EET was studied through modulating the exciton binding energy of g-C3N4. The different mechanisms of SET and EET for DCF degradation were predicted by DFT calculation, and further confirmed by their different degradation pathways. When EET played an important role, the rationality of some very popular radical scavengers, such as p-BQ, TEMPOL and furfuryl alcohol must be reconsidered. In addition, humic acid (HA) had a distinct effect on EET and SET. Specifically, HA enhanced the EET process through photosensitization, but suppressed SET through radical quenching effect. The effect of HA on DCF degradation depended on the contribution ratio of SET and ET.
Fracture-cave carbonate reservoirs represent a significant amount of oil and gas resources worldwide, while their intrinsic complex pore network, large caves and tectonic fractures bring challenges to reservoir characterizations and productions. Many models have been proposed to solve the pressure transient analysis (PTA) solutions for such reservoirs. With recent explorations, the position of fractures and caves can be determined by seismic data. However, models using the position information with the coexistence of discrete fractures and caves were not reported in the literature. This paper proposes a novel semi-analytical model based on the Boundary Element Method (BEM), to describe the transient pressure behavior of the fracture-cave carbonate reservoirs. Basically, the proposed model treats the cave edge as an inner boundary and includes the fracture-cave fluid interchanges. As a results, the model's solution is proved to be flexible for arbitrary cave and reservoir shape. A typical system consisting of one fracture and one case is discussed in detail. The result indicates the well location is the key factor to the pressure response, where the pressure response is mostly affected by the cave volume and fracture conductivity when the well is on the cave and fracture, respectively. The sensitivities of three major parameters on the pressure response are analyzed. In addition, the proposed model is applied in two field cases. The result shows the proposed model is reliable and accurate.