Modular polyoxometalate-layered double hydroxide composites as efficient oxidative catalysts

The exploitation of intercalation techniques in the field of two-dimensional layered materials offers unique opportunities for controlling chemical reactions in confined spaces and developing nanocomposites with desired functionality. In this paper, we demonstrate the exploitation of the novel and facile ‘one-pot’ anion-exchange method for the functionalization of layered double hydroxides (LDHs). As a proof of concept, we demonstrate the intercalation of a series of polyoxometalate (POM) clusters, Na3[PW12O40]•15H2O (Na3PW12), K6[P2W18O62]•14H2O (K6P2W18), and Na9LaW10O36•32H2O (Na9LaW10) into tris(hydroxymethyl)amino-methane (Tris) modified layered double hydroxides (LDHs) under ambient conditions without the necessity of degassing CO2. Investigation of the resultant intercalated materials of Tris-LDHs-PW12 (1), Tris-LDH-P2W18 (2), and Tris-LDH-LaW10 (3) for the degradation of methylene blue (MB), rhodamine B (RB) and crystal violet (CV) has been carried out, where Tris-LDH-PW12 reveals the best performance in the presence of H2O2. Additionally, degradation of a mixture of RB, MB and CV by Tris-LDH-PW12 follows the order of CV > MB > RB, which is directly related to the designed accessible area of the interlayer space. Also, the composite can be readily recycled and reused at least ten cycles without measurable decrease of activity

Efficient concurrent removal of sulfur and nitrogen contents from complex oil mixtures by using polyoxometalate-based composite materials

The increasingly stringent regulations in relation to the environmental impact of employed industrial processes make compulsory the development of alternative routes towards the reduction of sulfur and nitrogen contents in large scale chemical mixtures. Herein, we demonstrate for the first time the highly efficient application of polyoxometalate (POMs)/layered double hydroxide (LDHs) composites in deep desulfurization (1000 ppm) and denitrogenation (100 ppm) of a complex model oil system under mild conditions (65 °C), with a corresponding decrease of the content to less than 10 and 1 ppm, respectively. The high efficiency of the heterogeneous catalyst along with the high stability and easy recovery of the catalytic system renders them promising candidates for greener catalytic applications

An in vitro vesicle formation assay reveals cargo clients and factors that mediate vesicular trafficking

The fidelity of protein transport in the secretory pathway relies on the accurate sorting of proteins to their correct destinations. To deepen our understanding of the underlying molecular mechanisms, it is important to develop a robust approach to systematically reveal cargo proteins that depend on specific sorting machinery to be enriched into transport vesicles. Here, we used an in vitro assay that reconstitutes packaging of human cargo proteins into vesicles to quantify cargo capture. Quantitative mass spectrometry (MS) analyses of the isolated vesicles revealed cytosolic proteins that are associated with vesicle membranes in a GTP-dependent manner. We found that two of them, FAM84B (also known as LRAT domain containing 2 or LRATD2) and PRRC1, contain proline-rich domains and regulate anterograde trafficking. Further analyses revealed that PRRC1 is recruited to endoplasmic reticulum (ER) exit sites, interacts with the inner COPII coat, and its absence increases membrane association of COPII. In addition, we uncovered cargo proteins that depend on GTP hydrolysis to be captured into vesicles. Comparing control cells with cells depleted of the cargo receptors, SURF4 or ERGIC53, we revealed specific clients of each of these two export adaptors. Our results indicate that the vesicle formation assay in combination with quantitative MS analysis is a robust and powerful tool to uncover novel factors that mediate vesicular trafficking and to uncover cargo clients of specific cellular factors.</p

Facile immobilization of a Lewis acid polyoxometalate onto layered double hydroxides for highly efficient N-oxidation of pyridine based derivatives and denitrogenation

N-Oxides are a class of highly important compounds which are widely used as synthetic intermediates. In this paper, we demonstrate for the first time the use of a polyoxometalate (POM) based composite material, as highly efficient heterogeneous catalyst for the N-oxidation of pyridines and its derivatives in the presence of H2O2 at room temperature. The composite was prepared by intercalation of the [La(PW11O39)2]11- anion into a tris(hydroxymethyl)aminomethane (Tris) modified layered double hydroxides (LDHs). Additionally, the Tris-LDH-La(PW11)2–based catalyst has been employed for the denitrogenation of a model oil mixture in the presence of [bmim]BF4 and H2O2. Deep denitrogenation can be achieved in 40 minutes at 75 °C. Finally, the heterogeneous catalyst can be easily recovered and reused at least ten times without measurable decrease of the catalytic activity and disintegration of the Tris-LDH-La(PW11)2 structure

Polyoxometalates Hosted in Layered Double Hydroxides: Highly Enhanced Catalytic Activity and Selectivity in Sulfoxidation of Sulfides

Layered double hydroxides (LDHs) are a class of layered materials with tunable interlayer galleries. In this paper, a series of Mg₃Al–P₂W₁₇X (X = Mn^III, Fe^III, Zn^II, Co^II, Cu^II, Ni^II) have been prepared successfully by intercalating the polyoxometalate (POM) of [α₂-P₂W₁₇O₆₁(X·OH₂)]^<i>n</i>− ([P₂W₁₇X]^<i>n</i>−, <i>n</i> = 7 or 8) into a Mg₃Al–suberic precursor. Catalytic tests for H₂O₂-based sulfoxidation of various sulfides demonstrate that Mg₃Al–P₂W₁₇Zn exhibits better catalytic efficiency and selectivity than pure POM or LDH precursors under mild conditions. The uniform and well-ordered dispersion of POM in the confined gallery of LDHs and the multiple interactions between POMs and LDHs contribute to the excellent catalytic performance. Moreover, Mg₃Al–P₂W₁₇Zn is stable and can be easily separated from the reaction system. The recycled Mg₃Al–P₂W₁₇Zn maintains both the intact structures of the POM anion and LDHs. The scaled-up experiment provides further support for its potential use for industrial applications

Nutritional Programming of the Lifespan of Male Drosophila by Activating FOXO on Larval Low-Nutrient Diet

Nutrition during the developmental stages has long-term effects on adult physiology, disease and lifespan, and is termed nutritional programming. However, the underlying molecular mechanisms of nutritional programming are not yet well understood. In this study, we showed that developmental diets could regulate the lifespan of adult Drosophila in a way that interacts with various adult diets during development and adulthood. Importantly, we demonstrated that a developmental low-yeast diet (0.2SY) extended both the health span and lifespan of male flies under nutrient-replete conditions in adulthood through nutritional programming. Males with a low-yeast diets during developmental stages had a better resistance to starvation and lessened decline of climbing ability with age in adulthood. Critically, we revealed that the activity of the Drosophila transcription factor FOXO (dFOXO) was upregulated in adult males under developmental low-nutrient conditions. The knockdown of dFOXO, with both ubiquitous and fat-body-specific patterns, can completely abolish the lifespan-extending effect from the larval low-yeast diet. Ultimately, we identify that the developmental diet achieved the nutritional programming of the lifespan of adult males by modulating the activity of dFOXO in Drosophila. Together, these results provide molecular evidence that the nutrition in the early life of animals could program the health of their later life and their longevity

MnO2 as an Effective Sintering Aid for Difficult-to-Sinter LiTaO3-based Ceramics: Densification and Dielectric Properties

10.1016/j.jallcom.2020.154546Journal of Alloys and Compounds82915454

Iron metabolism in aging and age-related diseases

Iron is a trace metal element necessary to maintain life and is also involved in a variety of biological processes. Aging refers to the natural life process in which the physiological functions of the various systems, organs, and tissues decline, affected by genetic and environmental factors. Therefore, it is imperative to investigate the relationship between iron metabolism and aging-related diseases, including neurodegenerative diseases. During aging, the accumulation of nonheme iron destroys the stability of the intracellular environment. The destruction of iron homeostasis can induce cell damage by producing hydroxyl free radicals, leading to mitochondrial dysfunction, brain aging, and even organismal aging. In this review, we have briefly summarized the role of the metabolic process of iron in the body, then discussed recent developments of iron metabolism in aging and age-related neurodegenerative diseases, and finally, explored some iron chelators as treatment strategies for those disorders. Understanding the roles of iron metabolism in aging and neurodegenerative diseases will fill the knowledge gap in the field. This review could provide new insights into the research on iron metabolism and age-related neurodegenerative diseases

Quantifying the nucleation effect of correlated matrix grains in sintered Nd-Fe-B permanent magnets

© 2019 Elsevier B.V. The long-standing issue-the ferromagnetic coupling of adjacent Nd2Fe14B matrix grains across grain boundaries severely impedes further coercivity enhancement of sintered Nd-Fe-B permanent magnets. However, the quantitative role of the ferromagnetic coupling across grain boundaries on the coercivity degradation of sintered Nd-Fe-B magnets is still not well understood. Here, we quantified the nucleation effect of correlated (ferromagnetically coupled) matrix grains in sintered Nd-Fe-B magnets by integrating electron backscatter diffraction, energy dispersive spectroscopy, atom probe tomography, and high-resolution magnetic force microscopy in conjunction with micromagnetic simulations. We revealed that (1) the de-nucleation effect of correlated matrix grains (αψ) across intergranular grain boundaries is linearly enhanced with the increasing thickness (d) of grain boundaries (αψ = kd + l) and k is reduced with increasing exchange stiffness of these grain boundaries when the d is comparable to the domain wall width of the Nd2Fe14B matrix grains in sintered Nd-Fe-B magnets; (2) The thickness variation of the ferromagnetic grain boundary at the nanoscale is harmful to achieving high intrinsic coercivity of sintered Nd-Fe-B magnets; (3) The nucleation field is reduced if there is a little misalignment between correlated (ferromagnetically coupled) matrix grains. These findings shed light on grain boundary engineering at the nanoscale for enhancing the coercivity of Nd-Fe-B permanent magnets

The Sufficiency of Off-Policyness and Soft Clipping: PPO Is Still Insufficient according to an Off-Policy Measure

The popular Proximal Policy Optimization (PPO) algorithm approximates the solution in a clipped policy space. Does there exist better policies outside of this space? By using a novel surrogate objective that employs the sigmoid function (which provides an interesting way of exploration), we found that the answer is "YES", and the better policies are in fact located very far from the clipped space. We show that PPO is insufficient in "off-policyness", according to an off-policy metric called DEON. Our algorithm explores in a much larger policy space than PPO, and it maximizes the Conservative Policy Iteration (CPI) objective better than PPO during training. To the best of our knowledge, all current PPO methods have the clipping operation and optimize in the clipped policy space. Our method is the first of this kind, which advances the understanding of CPI optimization and policy gradient methods. Code is available at https://github.com/raincchio/P3O