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Over the past decade, deep neural networks have demonstrated significant success using the training scheme that involves mini-batch stochastic gradient descent on extensive datasets. Expanding upon this accomplishment, there has been a surge in research exploring the application of neural networks in other learning scenarios. One notable framework that has garnered significant attention is meta-learning. Often described as "learning to learn," meta-learning is a data-driven approach to optimize the learning algorithm. Other branches of interest are continual learning and online learning, both of which involve incrementally updating a model with streaming data. While these frameworks were initially developed independently, recent works have started investigating their combinations, proposing novel problem settings and learning algorithms. However, due to the elevated complexity and lack of unified terminology, discerning differences between the learning frameworks can be challenging even for experienced researchers. To facilitate a clear understanding, this paper provides a comprehensive survey that organizes various problem settings using consistent terminology and formal descriptions. By offering an overview of these learning paradigms, our work aims to foster further advancements in this promising area of research.
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A new topology previously unknown in metal-organic frameworks (MOFs) provides an important clue to uncovering a new series of polyhedral MOFs. We report a novel MOF crystallized in a parsimonious mep topology based on Frank-Kasper (FK) polyhedra. The distribution of angles in a tetrahedral arrangement (T-O-T) is crucial for the formation of FK polyhedra in mep topology. This finding led us to investigate the T-O-T angle distribution in related zeolites and zeolitic imidazolate frameworks (ZIFs). Unlike zeolites, it is extremely difficult to achieve high T-O-T angles in ZIFs, which prevents the formation of some FK topologies. Density functional theory (DFT) total energy calculations support a correlation between T-O-T angles and the feasibility of new tetrahedron-based FK frameworks. This result may lead to innovative ways of accessing new cellular topologies by simple chemical tweaking of T-O-T angles.
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Machines have continually developed with the needs of daily life and industrial applications. While the careful design of molecular-scale devices often displays enhanced properties along with mechanical movements, controlling mechanics within solid-state molecular structures remains a significant challenge. Here, we explore the distinct mechanical properties of zeolitic imidazolate frameworks (ZIFs)-frameworks that contain hidden mechanical components. Using a combination of experimental and theoretical approaches, we uncover the machine-like capabilities of ZIFs, wherein connected composite building units operate similarly to a mechanical linkage system. Importantly, this research suggests that certain ZIF subunits act as core mechanical components, paving an innovative view for the future design of solid-state molecular machines.
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Aryl fluorosulfates have emerged as versatile SuFExable substrates, harnessing the reactivity of the S-F bond. In this study, we unveil their alternative synthetic utility in nickel-catalyzed borylation via C-O bond activation. This method highlights mild reaction conditions, a broad substrate scope, and moderate functional group tolerance, rendering it a practical and appealing approach for synthesizing a diverse array of aryl boronate esters. Furthermore, computational analysis sheds light on the reaction pathways, uncovering the participation of LNi(0) and LNi(II)ArX species. This insight is supported by the 31P NMR reaction monitoring along with isolation and single-crystal X-ray structural elucidation of well-defined arylnickel(II) intermediates obtained from the oxidative addition of aryl fluorosulfates. A comprehensive investigation, merging experimental and computational approaches, deepens our understanding of the alternative reactivity of SuFExable substrates.
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Herein, synthesizable candidate topologies to form zeolitic imidazolate frameworks (ZIFs) are efficiently identified from over 2 000 000 hypothetical structures in zeolite databases, using structural descriptors extracted from known ZIFs. A combination of intuition-based structural descriptors, such as ring patterns, node numbers, and TOT bridging angles (T = tetrahedral metal nodes in zeolites and ZIFs), is used as data filters to eliminate topologies infeasible for ZIF formation. Carefully chosen structural descriptors facilitate the prediction of plausible ZIF topologies. To investigate potential applications as porous ZIFs, this work performs hydrogen adsorption screening and suggested notable target ZIFs. The collection of new plausible ZIFs, derived from the combined descriptors, will be a structural blueprint for synthetic chemists.
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Conventional synthetic methods to yield polycyclic heteroarenes have largely relied on metal-mediated arylation reactions requiring pre-functionalised substrates. However, the functionalisation of unactivated azines has been restricted because of their intrinsic low reactivity. Herein, we report a transition-metal-free, radical relay π-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts. Mechanistic and electron paramagnetic resonance studies provide evidence for the in situ generation of organic electron donors, while chemical trapping and electrochemical experiments implicate an iodanyl radical intermediate serving as a formal biaryl radical equivalent. This intermediate, formed by one-electron reduction of the cyclic iodonium salt, acts as the key intermediate driving the Minisci-type arylation reaction. The synthetic utility of this radical-based annulative π-extension method is highlighted by the preparation of an N-doped heptacyclic nanographene fragment through fourfold C-H arylation.
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The energetic properties of multicomponent explosive materials can be altered for high detonation capabilities and minimized safety risk by changing their building components. We synthesized energetic coordination polymers (ECPs) using a 5,5'-bis(tetrazole)-1,1'-diolate linker and a N,N-dimethylacetamide (DMA) solvent, together with Cu and Mn metal cations. The new compounds, ECP-1 and ECP-2, contain two different types of 1D chain structures, straight and helical. We have conducted comprehensive studies on these ECP structures, energetic properties, and sensitivity and found excellent insensitivity owing to the long chain-to-chain distances created by the DMA solvent molecules. The results indicate that the metals as well as solvents used are crucial components influencing both the structure and energetic properties.
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α,ß-Unsaturated ketones are common feedstocks for the synthesis of fine chemicals, pharmaceuticals, and natural products. Transition metal-catalysed hydroacylation reactions of alkynes using aldehydes have been recognised as an atom-economical route to access α,ß-unsaturated ketones through chemoselective aldehydic C-H activation. However, the previously reported hydroacylation reactions using rhodium, cobalt, or ruthenium catalysts require chelating moiety-bearing aldehydes to prevent decarbonylation of acyl-metal-hydride complexes. Herein, we report a nickel-catalysed anti-Markovnikov selective coupling process to afford non-tethered E-enones from terminal alkynes and S-2-pyridyl thioesters in the presence of zinc metal as a reducing agent. Utilization of a readily available thioester as an acylating agent and water as a proton donor enables the mechanistically distinctive and aldehyde-free hydroacylation of terminal alkynes. This non-chelation-controlled approach features mild reaction conditions, high step economy, and excellent regio- and stereoselectivity.
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Metal-organic polyhedra are a member of metal-organic materials, and are together with metal-organic frameworks utilized as emerging porous platforms for numerous applications in energy- and bio-related sciences. However, metal-organic polyhedra have been significantly underexplored, unlike their metal-organic framework counterparts. In this review, we will cover the topologies and the classification of metal-organic polyhedra and share several suggestions, which might be useful to synthetic chemists regarding the future directions in this rapid-growing field.
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An isostructural series of flexible metal-organic frameworks based on macrocycles having diverse pendant arms was developed to tune flexibility depending on functional groups. The pendant arms directing into the pores were found to play a key role in imparting different gate-opening behaviours in the threshold pressure and sorption capacity upon interaction with guest molecules.
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Coordination-driven assembly has been widely successful in the synthesis of metallocages and used for many applications, such as catalysis. However, studies on CO2 adsorption with metallocages have been rarely conducted, compared to other well-known cage-type materials, such as porous organic cages. In this study, a rational choice of ligand and metal led to the synthesis of a Zr6L3-type metallocage, exhibiting exceptional CO2 adsorption properties. CO2 adsorption experiments revealed that the metallocage shows highly selective adsorption of CO2 over N2 with high CO2 binding energy. Density functional theory calculations uncovered the origin of this exceptional affinity for CO2 over N2.
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We determined the effect of ketosis treatment with propylene glycol (PG) or PG plus l-carnitine and methionine (Metabolase®, Fatro, Bologna, Italy) on the resolution, postpartum health, milk yield, and reproductive performances of dairy cows. Blood from 475 Holstein cows was collected weekly until 4 weeks after calving to measure blood ß-hydroxybutyrate (BHBA) concentrations. Cows with blood BHBA concentration ≥1.2 mmol/L were diagnosed with ketosis and were enrolled. One hundred and fifty cows diagnosed with ketosis were randomly assigned to three treatment groups (Day 0): (1) PG (300 g, PO) for 3 days (PG group, n = 50), (2) PG (300 g, PO) plus l-carnitine (1.25 g) plus methionine (5 g, IV) for 3 days (PG + CM group, n = 50), and (3) no treatment (control group, n = 50). On Day 3, blood was collected to evaluate whether the ketosis had resolved. Cows in the PG and PG + CM groups with blood BHBA ≥1.2 mmol/L were retreated for an additional 2 days, and then blood BHBA concentration was evaluated on Days 5 and 10. Blood glucose and haptoglobin concentrations, rumen fill score (RFS), and body condition score (BCS) were measured on Days 0, 3, 5, and 10. Postpartum complications, milk yield during the first 2 months, and reproductive outcomes were evaluated. The probability of resolution from ketosis was higher (P < 0.05) in the PG + CM group than in the control group on Days 3, 5, and 10 (odds ratio: 2.6-6.3). Blood BHBA in the PG + CM group was lower (P < 0.05) than that of the control group on Days 3 and 5, whereas blood glucose in the PG + CM group was higher (P < 0.05) than that of the control group on Days 3 and 5. RFS in the PG and PG + CM groups was higher than that of the control group on Day 10 (P < 0.01), while BCS loss from Day 0-10 in the control group was higher than those of the PG and PG + CM groups (P < 0.05). Milk yields on the 30th and 60th days postpartum were higher in the PG + CM group than the control and PG groups (P < 0.05). Postpartum complications and intervals between calving and first postpartum insemination or pregnancy did not differ among the groups (P > 0.05). In conclusion, treatment of dairy cows with PG plus l-carnitine and methionine improved the chances of resolution of ketosis and increased milk yield, while affecting neither the incidence of postpartum complications nor reproductive performance.
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Carnitina/uso terapéutico , Enfermedades de los Bovinos/tratamiento farmacológico , Cetosis/veterinaria , Lactancia/fisiología , Metionina/uso terapéutico , Propilenglicol/uso terapéutico , Ácido 3-Hidroxibutírico/sangre , Animales , Carnitina/administración & dosificación , Bovinos , Femenino , Haptoglobinas/metabolismo , Metionina/administración & dosificación , Leche/fisiología , Periodo Posparto , Embarazo , Propilenglicol/administración & dosificaciónRESUMEN
For centuries, Corydalis Rhizoma has been used in Korean traditional medicine. Tetrahydropalmatine is an alkaloid compound and a prominent anti-inflammatory agent found in plants, including Corydalis yanhusuo. However, the therapeutic mechanisms of tetrahydropalmatine are still not well understood. To provide insight into the biological effects of tetrahydropalmatine, we examined its influence on lipopolysaccharide (LPS)-induced interleukin (IL)-8 production in the human monocytic cell line THP-1. In the present study, IL-8 production was measured using enzyme-linked immunosorbent assay, reverse transcription-polymerase chain reaction, and mitogen-activated protein kinase (MAPK) activation, as determined by western blot analysis. Tetrahydropalmatine inhibited LPS-induced IL-8 production in a dose-dependent manner. Furthermore, tetrahydropalmatine inhibited extracellular signal-regulated kinase and p38 MAPK phosphorylation, which suggests that tetrahydropalmatine inhibits IL-8 secretion by blocking MAPK phosphorylation. Taken together, these findings may help elucidate the mechanism by which tetrahydropalmatine modulates THP-1 cell activation under inflammatory conditions.