Aggregation induced-emission
(AIE) and antenna effects are important
luminescence behaviors. Thus, investigating their emission mechanisms
and revealing their behaviors have become critical but challenging.
Here we design and prepare metal–organic frameworks (MOFs)
with an AIE ligand (i.e., tetrakis(4-carboxyphenyl)pyrazine (L1)) and Ln3+ ions (including Eu3+,
Tb3+, and Gd3+). The emission from L1 is gradually enhanced during the formation of the MOFs because coordination
restricts the intramolecular rotation. Thus, the emission is called
as coordination-induced emission (CIE) with the same restriction of
intramolecular rotation mechanism as AIE. Meanwhile, benzene rings
twist to adapt to the MOFs’ rigid structure, so the emission
blueshifts gradually, as an additional evidence of CIE. Both AIE and
CIE are “rotation-restricted emission (RRE)”. Eu3+ ions exhibit the strongest emission with gradually enhanced
intensity during the formation of L1-Eu MOF. Combined
with emission properties from Tb3+ and Gd3+ ions,
the antenna effect is verified. We also validate the conditions for
the efficient sensitization of Ln3+ ions experimentally
and refresh the threshold value of the energy gap between triplet
state of a ligand and excited state of Ln3+ ions to 3000
cm–1. Thus, RRE and antenna effects are revealed
and validated simultaneously. Because CIE of L1 and antenna
effect emission from Eu3+ ions are enhanced simultaneously
as strong dual emissions, ratiometric fluorescence detection is realized
with the detection of arginine as a model. Our results incorporate
AIE and CIE into RRE, which provides explicit information for the
construction and application of emission systems with AIE ligands
as building blocks. MOFs are also extended to explore the emission
mechanism and the energy transfer between ligands and metal ions.
Heatmap regression with a deep network has become one of the mainstream approaches to localize facial landmarks. However, the loss function for heatmap regression is rarely studied. In this paper, we analyze the ideal loss function properties for heatmap regression in face alignment problems. Then we propose a novel loss function, named Adaptive Wing loss, that is able to adapt its shape to different types of ground truth heatmap pixels. This adaptability penalizes loss more on foreground pixels while less on background pixels. To address the imbalance between foreground and background pixels, we also propose Weighted Loss Map, which assigns high weights on foreground and difficult background pixels to help training process focus more on pixels that are crucial to landmark localization. To further improve face alignment accuracy, we introduce boundary prediction and CoordConv with boundary coordinates. Extensive experiments on different benchmarks, including COFW, 300W and WFLW, show our approach outperforms the state-of-the-art by a significant margin on various evaluation metrics. Besides, the Adaptive Wing loss also helps other heatmap regression tasks. Code will be made publicly available at https://github.com/ protossw512/AdaptiveWingLoss.
Aggregation-caused quenching (ACQ) is often observed in covalent organic frameworks (COFs) for their low emission. Here, we propose that limited COF layers form on UiO-66 to eliminate the ACQ by the formation of UiO@COF composites. UiO-66 is selected because this metal−organic framework (MOF) is easily prepared in nanosize with Zr 4+ ion and 2-aminoterephthalic acid (BDC-NH 2 ). The high affinity of the Zr 4+ ion to phosphate species improves sensing selectivity. The surface −NH 2 reacts with 2,4,6triformylphloroglucinol (Tp) to integrate COF1 and COF2, which are prepared with Tp and phenylenediamine or tetraamino-tetraphenylethylene, respectively. The hydrogen bond formed between the hydroxyl group in Tp and imine nitrogen realizes excited-state intramolecular proton transfer; therefore, multiemission is observed from the enol and keto states of the COFs and UiO-66 at 360, 470, and 613 nm for UiO@COF1 and at 370, 470, and 572 nm for UiO@COF2. When phosphate ion is added in the composites, the emissions from the COFs keep stable, while that from UiO-66 is enhanced. However, adenosine-5′-triphosphate (ATP) improves the emissions from UiO-66 and COF's enol state, but that from the keto state keeps stable. The differentiation and ratiometric fluorescence detection of ATP and phosphate ion are therefore realized with the multiemission, the affinity of Zr 4+ ions, and the structural selectivity of the COFs. Thus, UiO@COF is a novel strategy to integrate multiemission, affinity, and structural selectivity to improve the sensing performance for differentiation and ratiometric detection.
Heterogeneous hydrogenation reactions are of great importance for chemical upgrading and synthesis, but still face the challenges of controlling selectivity and long‐term stability. To improve the catalytic performance, many hydrogenation reactions utilize special yolk/core–shell nanoreactors (YCSNs) with unique architectures and advantageous properties. This work presents the developmental and technological challenges in the preparation of YCSNs that are potentially useful for hydrogenation reactions, and provides a summary of the properties of these materials. The work also addresses the scientific challenges in applications of these YCSNs in various gas and liquid‐phase hydrogenation reactions. The catalyst structures, catalytic performance, structure–performance relationships, reaction mechanisms, and unsolved problems are discussed too. Also, a brief outlook and opportunities for future research in this field are presented. This work on the advancements in YCSNs might inspire the creation of new materials with desired structures for achieving maximal hydrogenation performances.
Designing polymeric photocatalysts at the molecular level to modulate the photogenerated charge behavior is a promising and challenging strategy for efficient hydrogen peroxide (H 2 O 2 ) photosynthesis.Here, we introduce electron-deficient 1,4-dihydroxyanthraquinone (DHAQ) into the framework of resorcinolformaldehyde (RF) resin, which modulates the donor/ acceptor ratio from the perspective of molecular design for promoting the charge separation. Interestingly, H 2 O 2 can be produced via oxygen reduction and water oxidation pathways, verified by isotopic labeling and in situ characterization techniques. Density functional theory (DFT) calculations elucidate that DHAQ can reduce the energy barrier for H 2 O 2 production. RF-DHAQ exhibits excellent overall photosynthesis of H 2 O 2 with a solar-to-chemical conversion (SCC) efficiency exceeding 1.2 %. This work opens a new avenue to design polymeric photocatalysts at the molecular level for high-efficiency artificial photosynthesis.
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