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Development of effective targeted nanoparticle (TNP) therapeutics requires rational design of targeted and endosomolytic moieties. Nevertheless, endosomal escape of TNPs is poorly understood, relying on extrapolation of knowledge from nontargeted (NP) systems. Here, we describe how incorporation of targeting elements on endosomolytic nanoparticles alters the endosomal escape mechanism. We demonstrated that NP and TNP systems react differently to addition of precise length oligohistidines and showcase the effects of alternating spatial arrangements of targeting and endosomolytic elements. The results established that these elements act cooperatively and must be incorporated as individual moieties, rather than a single multifunctional moiety, for optimal internalization by target cells.Developing spatially controlled and universal p-type doping of transition-metal dichalcogenides (TMDs) is critical for optoelectronics. Here, a facile and universal p-doping strategy via Sn4+ ions exchanging is proposed and the p-doping of PdSe2 is demonstrated systematically as the example. The polarity of PdSe2 can be modulated from n-type to bipolar and p-type precisely by changing the concentration of SnCl4 solution. The modulation effectively reduces the electron concentration and improves the work function by ∼72 meV. In addition, the solution-processable route makes the spatially controlled doping possible, which is demonstrated by constructing the lateral PdSe2 p-n homojunction with rectification behavior and photovoltaic effect. This p-doping method has been further proved in modulating various TMDs including WSe2, WS2, ReSe2, MoSe2, MoTe2, and PtSe2. This spatially controlled and universal method based on Sn atoms substitution realizes p-type doping of TMDs.Low-valent transition metalates─anionic, electronic-rich organometallic complexes─comprise a class of highly reactive chemical reagents that find integral applications in organic synthesis, small-molecule activation, transient species stabilization, and M-E bond formation, among others. The inherent reactivity of such electron-rich metal centers has necessitated the widespread use of strong backbonding ligands, particularly carbonyls, to aid in the isolation and handling of metalate reagents, albeit sometimes at the expense of partially masking their full reactivity. However, recent synthetic explorations into transition-metalate complexes devoid of archetypic back-bonding ligands have led to the discovery of highly reactive metalates capable of performing a variety of novel chemical transformations.Building on our group's long-standing interest in reactive organometallic species, a series of rational progressions in early-to-middle transition-metal chemistry ultimately led to our isolation of a rhenium(I) β-duce additional reactive organometallic species capable of stabilizing unique structural motifs and performing novel and unusual chemical transformations.Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C-C Suzuki-Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9'-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption-desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki-Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.The interfacial nanoparticle compatibilization (INC) strategy has opened up a promising avenue toward simultaneous functionalization and interfacial engineering of immiscible polymer blends. While the INC mechanism has been well developed recently, few investigations have focused on rigid nanoplatelets because of the inherent steric hindrance of the surface-grafted polymer chains. Herein, surface-modified rigid nanoplatelets have been incorporated into an immiscible poly(l-lactide) (PLLA)/poly(butylene succinate) (PBSU) blend. It is demonstrated that the strong interfacial adhesion between PLLA and PBSU phases is promoted via molecular entanglements of the grafted chains on the surface of nanoplatelets with the individual components. A refined phase morphology with improved mechanical properties can be achieved with the addition of 5 wt % modified Gibbsite nanoplatelets. It was further found that the stiffness of nanoplatelets can change the geometry of the interface significantly. It is, therefore, indicated that the simultaneous interface strengthening and interfacial curvature controlling of rigid nanoplatelets originate from the selective swelling/collapse of the in situ-formed PLLA and PBSU grafts within the corresponding phase at the interface. Such a mechanism is confirmed by the Monte Carlo simulations. This work provides new opportunities for the fabrication of advanced polymer blend nanocomposites.The influence of different air entrainment conditions on the emissions of particulate matter from fire whirls was investigated by igniting a diesel fuel pool, 0.7 m in diameter, within a four-walled enclosure. Four different natural entrainment conditions resulted when gap sizes in the walls were varied between 0.35 and 0.65 m. In addition, three forced-entrainment conditions were created by holding the gap width constant and varying the air-entrainment velocity using fans positioned at each of the four gaps. OSMI-1 purchase The concentration of particulates was measured for these seven conditions, and one pool fire condition for comparison. For fire whirls under natural entrainment, the emission factor of total particulate matter, EFPM, was lower than that for pool fires, and decreased with increasing gap size. Fire whirls under mild levels of forced entrainment showed the lowest values of EFPM, but as the level of forced entrainment was increased, EFPM increased steadily to a value higher than that of pool fires. The reduction in EFPM is attributed to a combination of leaner stoichiometry and the interaction between the entrainment and the instantaneous burning rate. Thus, for a given pool diameter, an optimum value of entrainment velocity exists where the EFPM is lowest. Considerations for utilizing whirling flames to reduce airborne particulate emissions from in situ burning are discussed.Hierarchically porous metal-organic frameworks (HP-MOFs) are promising in many applications. However, most previous studies focus on HP-MOFs with two kinds of pore structures. Herein, a strategy for efficient construction of HP-MOFs possessing macro-meso-micropores using template-assisted spray drying followed by etching process is proposed. Taking ZIF-8 as an example, using polystyrene (PS) templates, the complete HP-ZIF-8 with all the three categories of pores can be easily fabricated. The close arrangement of intrinsic microporous nanosized ZIF-8 (N-ZIF-8) in the spray drying process results in the creation of mesopores, while the macropores are further generated after the removal of PS templates. The structures of macropores and mesopores can be easily adjusted by altering the size and proportion of PS and the size of N-ZIF-8, respectively. Furthermore, this method is extended to the preparation of HP-HKUST-1. As a proof-of-concept, HP-ZIF-8 displays excellent catalytic properties in Knoevenagel reaction owing to its unique pore features. Compared with conventional microsized ZIF-8 (M-ZIF-8) with similar size, HP-ZIF-8 achieves the significantly increased conversion of benzaldehyde from 55% to 100% within 3 h, and shows better recycling performance than N-ZIF-8.Biomacromolecules featuring aggregation-induced-emission (AIE) characteristics generally present new properties and performances that are silent in the molecular state, providing endless possibilities for the evolution of biomedical applications. Tremendous achievements based on the research of AIE-active biomacromolecules have been made in synthetic exploration, material development, and practical applications. In this Perspective, we give a brief account in the development of AIE-active biomacromolecules. Remarkable progresses have been made in the exploration of AIE-active biomacromolecule preparation, structure-property relationships, and the relevant biomedical applications. The existing challenges and promising opportunities, as well as the future directions in AIE-active biomacromolecule research, are also discussed. It is expected that this Perspective can act as a trigger for the innovation of AIE-active biomacromolecule research and aggregate science.The development of green and renewable materials has attracted increasing attention in recent years. Hence, biocomposite-based packaging materials have been investigated to replace petrochemical materials in several industries, such as the food packaging and electronics packaging industries. The tensile and thermal properties of biocomposite-based packaging materials composed of polylactic acid and plant fiber were mainly investigated in the current literature, but fewer studies on the improvement of water resistance and water vapor/oxygen barrier properties of composite materials were performed. Herein, we describe a composite film comprising TBFP [a mixture of bamboo fiber powder (BFP) and silica aerogel powder] that was combined with modified polylactic acid (MPLA) in a melt-mixing process. The structure, morphology, tensile strength, thermal properties, water absorption properties, water vapor/oxygen barrier effect, cytocompatibility, and biodegradability of the composites were characterized. MPLA and TBFan be used as packing materials in many perspectives.Slow kinetics in the oxygen evolution reaction (OER) remains a Gordian knot to develop an efficient and cost-effective electrocatalyst in electrochemical water splitting. In recent studies, either a synergistic effect on multimetallic catalysts or spin polarization in ferromagnetic materials is considered as a desirable way to improve water electrolysis. Herein, the OER performance of amorphous FeNiCo-based multimetallic catalysts with adjustable composition was investigated from the perspective of atomic structure. Mössbauer spectra results demonstrate that the OER activities exhibit a significant dependence on the local structure of catalysts in which a catalyst with a high content of Fe clusters of low coordination numbers tends to obtain higher activity. Furthermore, benefiting from the spin polarization of these ferromagnetic catalysts, the OER activity is notably enhanced in the presence of a magnetic field. In particular, overpotential reduction exceeding 20 mV (above 100 mA cm-2) in alkaline OER performance is observed for strong ferromagnetic catalysts in comparison with the weak ferromagnetic ones.
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