The rational design of metal-organic frameworks (MOFs) with hollow features and tunable porosity at the nanoscale can enhance their intrinsic properties and stimulates increasing attentions. In this Communication, we demonstrate that methanol can affect the coordination mode of ZIF-67 in the presence of Co(2+) and induces a mild phase transformation under solvothermal conditions. By applying this transformation process to the ZIF-67@ZIF-8 core-shell structures, a well-defined hollow Zn/Co ZIF rhombic dodecahedron can be obtained. The manufacturing of hollow MOFs enables us to prepare a noble metal@MOF yolk-shell composite with controlled spatial distribution and morphology. The enhanced gas storage and porous confinement that originate from the hollow interior and coating of ZIF-8 confers this unique catalyst with superior activity and selectivity toward the semi-hydrogenation of acetylene.
Herein, a series of porous nano-structured carbocatalysts have been fused and decorated by Mo-based composites, such as Mo2 C, MoN, and MoP, to form a hybrid structures. Using the open porosity derived from the pyrolysis of metal-organic frameworks (MOFs), the highly dispersive MoO2 small nanoparticles can be deposited in porous carbon by chemical vapor deposition (CVD). Undergoing different treatments of carbonization, nitridation, and phosphorization, the Mo2 C-, MoN-, and MoP-decorated carbocatalysts can be selectively prepared with un-changed morphology. Among these Mo-based composites, the MoP@Porous carbon (MoP@PC) composites exhibited remarkable catalytic activity for the hydrogen evolution reaction (HER) in 0.5 m H2 SO4 aqueous solution versus MoO2 @PC, Mo2 C@PC, and MoN@PC. This study gives a promising family of multifunctional lab-on-a-particle architectures which shed light on energy conversion and fuel-cell catalysis.
The rational design of metal-organic frameworks (MOFs) with hollowf eatures and tunable porosity at the nanoscale can enhance their intrinsic properties and stimulates increasing attentions.I nt his Communication, we demonstrate that methanol can affect the coordination mode of ZIF-67 in the presence of Co 2+ and induces amild phase transformation under solvothermal conditions.B ya pplying this transformation process to the ZIF-67@ZIF-8 core-shell structures,awelldefined hollowZ n/Co ZIF rhombic dodecahedron can be obtained. The manufacturing of hollowM OFs enables us to prepare an oble metal@MOF yolk-shell composite with controlled spatial distribution and morphology.The enhanced gas storage and porous confinement that originate from the hollow interior and coating of ZIF-8 confers this unique catalyst with superior activity and selectivity towardthe semi-hydrogenation of acetylene.Toimpart new functionalities and properties,e normous efforts have been made to build metal-based composites such as metal/metal and metal/metal oxide composites. [1] Recently, the metal nanoparticles (NPs)@MOFs composite has shown alot of advantages as anew type of catalyst and thus became arising star. [2] Forexample,encapsulation of metal NPs within MOFs can prevent agglomeration and effectively enhance the thermodynamic stability. [3] Organic functional groups of MOFs could serve as Lewis base or acid to implement the metal sites in certain Lewis base-/acid-catalyzed processes. [4] Moreover,t he well-defined porous structure of MOFs can confer the shape-or size-selectivity properties if the dimension of reactants and products were carefully modulated. [5] However,w hen the catalytic process occurs inside the pores, the diffusion control by reactants or products should be taken into account. To this end, the hollow interior of MOFs would facilitate the diffusion of substrates onto the internal metal surface as well as the desorption of products. [6] To date,t he construction of hybrid metal@hollow MOFs,s imultaneously controlling their composition, morphology,a nd spatial distribution, are highly desired, but yet challenging. [7] Zeolite imidazolate frameworks (ZIF) are promising and widely used MOFs for heterogeneous catalysis due to their uniform pore size,w ell-defined morphology,a nd excellent chemical stability. [8] Thes trong coordination between metal ions and imidazolate enables the use of ZIFs in commonly used solvents and the structural integrity can survive even in water which is usually problematic for MOFs.H owever,t he construction of ah ollow interior in ZIFs,w hich will destroy the stable coordination bond, is facing tremendous challenges. Recent efforts in creating ZIF-based hollow or yolk-shell structures used at emplate such as ap olymer or oxides. [9] However,t he drastic process for template removal will damage the uniform ordered porous structure and distort the original rhombic dodecahedron morphology.Asaconsequence,t he as-prepared hollow ZIFs usually exhibit ap olycrystalline nature and problems like chan...
Herein, aseries of porous nano-structured carbocatalysts have been fused and decorated by Mo-based composites,s uch as Mo 2 C, MoN,a nd MoP,t of orm ah ybrid structures.U sing the open porosity derived from the pyrolysis of metal-organic frameworks (MOFs), the highly dispersive MoO 2 small nanoparticles can be deposited in porous carbon by chemical vapor deposition (CVD). Undergoing different treatments of carbonization, nitridation, and phosphorization, the Mo 2 C-, MoN-, and MoP-decorated carbocatalysts can be selectively prepared with un-changed morphology.A mong these Mo-based composites,t he MoP@Porous carbon (MoP@PC) composites exhibited remarkable catalytic activity for the hydrogen evolution reaction (HER) in 0.5 m H 2 SO 4 aqueous solution versus MoO 2 @PC,M o 2 C@PC,a nd MoN@PC.T his study gives ap romising family of multifunctional lab-on-a-particle architectures which shed light on energy conversion and fuel-cell catalysis.
MicroRNAs (miRNAs) have recently been recognized as targets for anti-metastatic therapy against cancer malignancy. Development of effective miRNA mediated therapies remains a challenge to both basic research and clinical practice. Here we presented the evidence for a miR-708-5p mediated replacement therapy against metastatic lung cancer. Expression of miR-708-5p was substantially reduced in metastatic lung cancer samples and cancer cell lines when compared to non-metastatic counterparts. Expression of the miRNA suppressed cell survival and metastasis in vitro through its direct target p21, and inhibited the PI3K/AKT pathway and stem cell-like characteristics of lung cancer cells. Systemic administration of this miRNA in a mouse model of NSCLC using polyethylenimine (PEI)-mediated delivery of unmodified miRNA mimics induced tumor specific apoptosis. It also effectively protected the tested animals from developing metastatic malignancy without causing any observed toxicity.The findings strongly support miR-708-5p as a novel and effective therapeutic agent against metastatic malignancy of non-small cell lung cancer.
Abstrac tWithi n the framework of Bayes i an stati stics, real izations or estimates of rock property fiel ds can be generated t a utomati c hist or y m atching of pro du ct i on d ata using a prior m o d e l to pr ovide regul ari zat i on . In t hi s c onte x a utomat i c bistor y m atching r equires t he minimiz ation of an obj ect ive fun ct ion which in cludes both m ode l an data mi s match te rm s . Fo r l arge sca le pr o blem s, t h e computati o nal effic i en cy and robustn ess of t h e op timiz a ti o a lgori t hm s u sed fo r minimizat ion ar e o f p aramount importan te . From a co mp ar ison of algorithms for a vari ety c bi s to ry m atc hi n g probl ems, a sca led limite d m emory Broyd en-Fletch er-Goldfarb-Sh a nno a lgo rithm was id entifie as the most pr o mi sin g fo r lar ge sca le optimi zat ion proble ms . Introductio nWe consider the application of automatic bistory matching to estimate or simulate reservoir model variables thé honor production data and are consistent with a prior geostatistical model . Reservoir variables may represer gridblock permeabilities and porosities, local or zonal transmissibility or pore volume multipliers, or geometri variables that describe the shape, size and location of objects . The Bayesian formulation of the problems considere here is identical to the one considered by Li et al . (2001), except that work considered only the Gauss-Newton (GN method and a modified Levenberg-Marquardt (MLM) algorithm for minimization . However, unless the number c model parameters or the number of data is relatively small, implementation of these methods in a way that requirE calculation of the sensitivity of each predicted data to Bach model parameter is impractical . Here, we compare variety of gradient-based algorithms on the basis of computational efficiency and memory requirements . Our goj is to identify optimization algorithms that can be applied for automatie bistory matching when the number c conditioning production data ranges Erom a few hundred to several thousand and the number of reservoir variable ranges Erom several hundred to tens of thousands . Although reparameterization methods, such as zonation, gra zones, pilot points, spectral decomposition, and subspace methods, are sometimes used to reduce the number c sensitivities calculated and the number of variables estimated directly, no model reparameterization is applied fc the problems considered in this paper .Quasi-Newton (variable metric) methods, which are based on generating an approximation to the inverse of th Hessian matrix, require only the gradient of the objective function and thus avoid the computation of individu sensitivity coefficients needed to directly form the Hessian matrix . Here, only the Broyden-Flecher-Goldfarb-Shann (BFGS) quasi-Newton method is considered since it bas proved to be more robust in practice than other algorithm : see Kolda et al . (1998) . It is well known that scaling can improve the convergente attributes of quasi-Newton (QN methods, and numerous suggestions have be...
Oxidative stress and neuroinflammation contribute significantly to the development and progression of diabetic retinopathy. Fenofibrate has received great attention as it benefits diabetic patients by reducing retinal laser requirement. Nuclear factor erythroid-2-related factor 2 (Nrf2) is a master regulator of anti-oxidative defense. Activation of nucleotide binding domain, leucine-rich repeat-containing receptor (NLR), pyrin domain-containing 3 (NLRP3) inflammasome plays a pivotal role in neuroinflammation. The purpose of this study is to determine whether fenofibrate protects retinas from oxidative damage and neuroinflammation via modulating the Nrf2 pathway and blocking NLRP3 inflammasome activation during diabetes. Diabetes is induced by intraperitoneal injection of streptozotocin in mice. Fenofibrate was given to mice in rodent chow. Upregulation of Nrf2 and NLRP3 inflammasome, enhanced ROS formation, and increased leukostasis and vascular leakage were observed in diabetic mouse retinas. Notably, Nrf2 and Caspase-1 were mainly colocalized with glutamine synthetase, one of the Mȕller cell markers. Fenofibrate further increased the expression of Nrf2 and its target gene NQO-1 and HO-1 and reduced ROS formation in diabetic retinas. In addition, retinal expression of NLRP3, Caspase-1 p20, IL-1β p17, and ICAM-1 were dramatically increased in vehicle-treated diabetic mice, which were abolished by fenofibrate intervention. Moreover, fenofibrate treatment also attenuated diabetes-induced retinal leukostasis and vascular leakage in mice. Taken together, fenofibrate attenuates oxidative stress and neuroinflammation in diabetic retinas, which is at least partially through modulating Nrf2 expression and NLRP3 inflammasome activation.
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