Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks: The case of squaramide

A well-established strategy to synthesize heterogeneous,metal-organic framework(MOF)catalysts that exhibit nanoconfinement effects,and specific pores with highly-localized catalytic sites,is to use organic linkers containing organocatalytic centers.Here,we report that by combining this linker approach with reticular chemistry,and exploiting three-dimensioanl(3D)MOF-structural data from the Cambridge Structural Database,we have designed four heterogeneous MOF-based catalysts for standard organic transformations.These programmable MOFs are isoreticular versions of pcu IRMOF-16,feu UiO-68 and pillared-pcu SNU-8X,the three most common topologies of MOFs built from the organic linker p.p'-terphenyldicarboxylic acid(tpdc).To synthesize the four squaramide-based MOFs,we designed and synthesized a linker,4,4’-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid(Sq_tpdc),which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers.Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena.Therefore,the four MOFs share the same organocatalytic squaramide moiety,but confine it within distinct pore environments.We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations:a Friedel-Crafts alkylation and an epoxide ring-opening.Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.     

Hedgehog Signalling Modulates Immune Response and Protects against Experimental Autoimmune Encephalomyelitis

The Hedgehog (Hh) pathway is essential for the embryonic development and homeostatic maintenance of many adult tissues and organs. It has also been associated with some functions of the innate and adaptive immune system. However, its involvement in the immune response has not been well determined. Here we study the role of Hh signalling in the modulation of the immune response by using the Ptch-1-LacZ^+/− mouse model (hereinafter referred to as ptch^+/−), in which the hemizygous inactivation of Patched-1, the Hh receptor gene, causes the constitutive activation of Hh response genes. The in vitro TCR stimulation of spleen and lymph node (LN) T cells showed increased levels of Th2 cytokines (IL-4 and IL-10) in ptch^+/−cells compared to control cells from wild-type (wt) littermates, suggesting that the Th2 phenotype is favoured by Hh pathway activation. In addition, CD4⁺ cells secreted less IL-17, and the establishment of the Th1 phenotype was impaired in ptch^+/− mice. Consistently, in response to an inflammatory challenge by the induction of experimental autoimmune encephalomyelitis (EAE), ptch^+/− mice showed milder clinical scores and more minor spinal cord damage than wt mice. These results demonstrate a role for the Hh/ptch pathway in immune response modulation and highlight the usefulness of the ptch^+/− mouse model for the study of T-cell-mediated diseases and for the search for new therapeutic strategies in inflammatory diseases.     

A loop-based approach in clustering and routing in Mobile Ad hoc NETworks

Although clustering is a convenient framework to enable traffic control and service support in Mobile Ad hoc NETworks （MANETs）, it is seldom adopted in practice due to the additional traffic overhead it leads to for the resource limited ad hoc network. In order to address this problem, we proposed a loop-based approach to combine clustering and routing. By employing loop topologies, topology information is disseminated with a loop instead of a single node, which provides better robustness, and the nature of a loop that there are two paths between each pair of nodes within a loop composed of setup procedure, regular procedure and emergent route recovering. suggests smart route recovery strategy. Our approach is recovery procedure to achieve clustering, routing and     

Analysis of the Content of Fatty Acid Methyl Esters in Biodiesel by Fourier-Transform Infrared Spectroscopy: Method and Comparison with Gas Chromatography

The increasing importance of sustainability in energy production has led to a global commitment to the use of fuels derived from renewable biological sources, such as biodiesel produced from plant crops or biomass residues, that do not compete with human food for their production. For a biofuel to be considered biodiesel, it must satisfy the specifications described in the UNE 14214, with the UNE-EN 14103 referring to the determination of fatty acid methyl ester content. This standard applies gas chromatography as an analytical technique. Gas chromatography is a widely used technique in the analysis of methyl ester although it has a number of drawbacks such as: long analysis times, a high consumption of high-quality gases and internal standards, does not allow the analysis of different compounds with the same column, etc. From an industrial production point of view, is necessary to know the fatty acid methyl ester content in biodiesel samples quickly. This paper studies the development of an analytical method using Fourier transform infrared spectroscopy (FTIR) as alternative to gas chromatography (GC), since it is a simple, rapid, and precise analytical technique to quantify fatty acid methyl ester content in biofuel samples.     

Electroconductive nylon 6 and copper composites

A study is reported on the effect of the filler size and concentration on the electrical resistivity, density, and hardness of composites made of copper powder embedded in nylon 6 matrix by means of compression molding. The electrical resistivity of the composites is > 10¹¹ ohm·cm unless the metal content reached the percolation threshold, beyond which the resistivity decreased markedly by as much as 10¹². The percolation concentration was found to decrease with a decrease in the average particle diameter. The density of the composites was measured and compared with values calculated assuming different void levels within the samples. However, there is no sharp variation in the density due to the onset of percolation. Furthermore, it is shown that a percolation concentration can be also defined in the hardness/metal concentration curves as the intercept of linear regression curves of the low and high metal content regimes, respectively.     

Interfacial area and mass transfer in carbon dioxide absorption in TEA aqueous solutions in a bubble column reactor

The hydrodynamic behaviour and mass transfer of carbon dioxide removal process by aqueous solutions of triethanolamine (TEA) are analysed. The experiments were made in a bubble column reactor (BCR) as gas–liquid contactor. The interfacial area and mass transfer coefficient were calculated by using a photographic method based on the bubble diameter determination. The influence of operation conditions, liquid phase nature and chemical reaction on the mass transfer coefficient and gas–liquid interfacial area has been also analysed.     

Mechanosynthesis and Thermal Stability of Piezoelectric Perovskite 0.92Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 Powders

The mechanosynthesis of piezoelectric perovskite 0.92Pb(Zn_1/3Nb_2/3)O₃–0.08PbTiO₃ (PZN–PT) by direct mechanochemical activation of the constituent oxides has been studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM). This and the PbO flux method are the only two procedures that have succeeded in synthesizing this phase, which has recently been shown to present very high electromechanical response. The thermal stability of the single perovskite phase powders has been studied by differential thermal analysis/thermogravimetry and by high-temperature XRD as a function of mechanical activation time and pressure. The phase was found to transform into a pyrochlore type structure at temperatures above 400°C. The transformation presented a significant time dependence, and it was slowed down by increasing mechanical activation time and by the application of pressures by hot pressing. Sintering experiments were accomplished and 85% density, 77% perovskite-phase ceramics were obtained after heating at 1000°C for 1 h. Hot pressing at this temperature failed to increase the percentage of perovskite phase. Results are discussed, and procedures for obtaining dense single-phase PZN–PT-based ceramics with ultrahigh piezoelectricity are proposed.     

Mechanosynthesis of the multiferroic cubic spinel Co2MnO4: Influence of the calcination temperature

Multiferroic materials showing magnetoelectric coupling are required in various technological applications. Many synthetical approaches can be used to improve the magnetic and/or electrical properties, in particular when the materials exhibit cationic valence fluctuations, as in the Co₂MnO₄ cubic spinel. In this compound, Co and Mn ions are in competition at the tetrahedral and octahedral positions, depending on their various oxidation states. The Co₂MnO₄ was prepared following two techniques: by a soft chemical route based on a modified polymer precursor method, and by a mechanoactivation route. Both approaches yield polycrystalline powders, but their crystallites sizes and particles morphologies differ as a function of the calcination conditions. The magnetic characterization (ZFC/FC cycles, ordering temperatures, ferromagnetic coercive fields and saturation magnetizations) showed that the synthesis procedure influenced the physical properties of Co₂MnO₄ mainly through the size of the magnetic domains, which play an important role on the magnetic interactions between the Co/Mn cations.     

Theoretical and Experimental Insight into the Mechanism for Spontaneous Vertical Growth of ReS2 Nanosheets

Rhenium disulfide (ReS₂) differs fundamentally from other group‐VI transition metal dichalcogenides (TMDs) due to its low structural symmetry, which results in its optical and electrical anisotropy. Although vertical growth is observed in some TMDs under special growth conditions, vertical growth in ReS₂ is very different in that it is highly spontaneous and substrate‐independent. In this study, the mechanism that underpins the thermodynamically favorable vertical growth mode of ReS₂ is uncovered. It is found that the governing mechanism for ReS₂ growth involves two distinct stages. In the first stage, ReS₂ grows parallel to the growth substrate, consistent with conventional TMD growth. However, subsequent vertical growth is nucleated at points on the lattice where Re atoms are “pinched” together. At such sites, an additional Re atom binds with the cluster of pinched Re atoms, leaving an under‐coordinated S atom protruding out of the ReS₂ plane. This under‐coordinated S is “reactive” and binds to free Re and S atoms, initiating growth in a direction perpendicular to the ReS₂ surface. The utility of such vertical ReS₂ arrays in applications where high surface‐to‐volume ratio and electric‐field enhancement are essential, such as surface enhanced Raman spectroscopy, field emission, and solar‐based disinfection of bacteria, is demonstrated.