259,216 research outputs found
Student Performance may not Improve when Universities are Choosier
We use unique administrative data from a leading Italian University to estimate whether the use of admission tests and conditional progression schemes are effective strategies to select high-performing students. Previous work has mainly focused on the effect of selectivity policies on widening university access by individuals from ethnic minorities and disadvantaged background.college student performance, college admission, institutional selectivity, difference-in-difference design
A Catalytic and Selective Scissoring Molecular Tool for Quadruplex Nucleic Acids
A copper complex embedded in the structure of a water-soluble naphthalene diimide has been designed to bind and cleave G-quadruplex DNA. We describe the properties of this ligand, including its catalytic activity in the generation of ROS. FRET melting, CD, NMR, gel sequencing, and mass spectrometry experiments highlight a unique and unexpected selectivity in cleaving G-quadruplex sequences. This selectivity relies both on the binding affinity and structural features of the targeted G-quadruplexes
Rational design of a polyoxometalate intercalated layered double hydroxide: highly efficient catalytic epoxidation of allylic alcohols under mild and solvent-free conditions
Intercalation catalysts, owing to their modular and accessible gallery and unique interlamellar chemical environment, have shown wide application in various catalytic reactions. However, the poor mass transfer between the active components of the intercalated catalysts and organic substrates is one of the challenges that limit their further application. Herein, we have developed a novel heterogeneous catalyst by intercalating the polyoxometalate (POM) of Na9LaW10O36⋅32 H2O (LaW10) into layered double hydroxides (LDHs), which have been covalently modified with ionic liquids (ILs). The intercalation catalyst demonstrates high activity and selectivity for the epoxidation of various allylic alcohols in the presence of H2O2. For example, trans-2-hexen-1-ol undergoes up to 96 % conversion and 99 % epoxide selectivity at 25 °C in 2.5 h. To the best of our knowledge, the Mg3Al−ILs−C8−LaW10 composite material constitutes one of the most efficient heterogeneous catalysts for the epoxidation of allylic alcohols (including the hydrophobic allylic alcohols with long alkyl chains) reported so far
Towards energetically viable asymmetric deprotonations : selectivity at more elevated temperatures with C2-symmetric magnesium bisamides
A novel chiral magnesium bisamide has enabled the development of effective asymmetric deprotonation protocols at substantially more elevated temperatures. This new, structurally simple, C2-symmetric magnesium complex displays excellent levels of asymmetric efficiency and energy reduction in the synthesis of enantioenriched enol silane
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Targeted polypharmacology: discovery of dual inhibitors of tyrosine and phosphoinositide kinases.
The clinical success of multitargeted kinase inhibitors has stimulated efforts to identify promiscuous drugs with optimal selectivity profiles. It remains unclear to what extent such drugs can be rationally designed, particularly for combinations of targets that are structurally divergent. Here we report the systematic discovery of molecules that potently inhibit both tyrosine kinases and phosphatidylinositol-3-OH kinases, two protein families that are among the most intensely pursued cancer drug targets. Through iterative chemical synthesis, X-ray crystallography and kinome-level biochemical profiling, we identified compounds that inhibit a spectrum of new target combinations in these two families. Crystal structures revealed that the dual selectivity of these molecules is controlled by a hydrophobic pocket conserved in both enzyme classes and accessible through a rotatable bond in the drug skeleton. We show that one compound, PP121, blocks the proliferation of tumor cells by direct inhibition of oncogenic tyrosine kinases and phosphatidylinositol-3-OH kinases. These molecules demonstrate the feasibility of accessing a chemical space that intersects two families of oncogenes
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Graphene-polyelectrolyte multilayer membranes with tunable structure and internal charge
One great advantage of graphene-polyelectrolyte multilayer (GPM) membranes is their tunable structure and internal charge for improved separation performance. In this study, we synthesized GO-dominant GPM membrane with internal negatively-charged domains, polyethyleneimine (PEI)-dominant GPM membrane with internal positively-charged domains and charge-balanced dense/loose GPM membranes by simply adjusting the ionic strength and pH of the GO and PEI solutions used in layer-by-layer membrane synthesis. A combined system of quartz crystal microbalance with dissipation (QCM-D) and ellipsometry was used to analyze the mass deposition, film thickness, and layer density of the GPM membranes. The performance of the GPM membranes were compared in terms of both permeability and selectivity to determine the optimal membrane structure and synthesis strategy. One effective strategy to improve the GPM membrane permeability-selectivity tradeoff is to assemble charge-balanced dense membranes under weak electrostatic interactions. This balanced membrane exhibits the highest MgCl2 selectivity (∼86%). Another effective strategy for improved cation removal is to create PEI-dominant membranes that provide internal positively-charged barrier to enhance cation selectivity without sacrificing water permeability. These findings shine lights on the development of a systematic approach to push the boundary of permeability-selectivity tradeoff for GPM membranes
Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies.
The combination of two different β-diketone ligands facilitates the size-controlled assembly of pure heterometallic [LnLn'Ln] linear compounds thanks to two different coordination sites present in the molecular scaffold. [HoCeHo], [ErCeEr], and [YbCeYb] analogues are presented here and are characterized both in the solid state and in solution, demonstrating the selectivity of this unique method to produce heterometallic 4f molecular entities
Safe design and operation of tank reactors for multiple-reaction networks: uniqueness and multiplicity
A method is developed to design a tank reactor in which a network of reactions is carried out. The network is a combination of parallel and consecutive reactions. The method ensures unique operation. Dimensionless groups are used which are either representative of properties of the reaction system or exclusively of the design and operating variables. In a plot of the optimal yield vs the dimensionless operating temperature the region is indicated where operation under conditions of uniqueness is feasible. The method is illustrated with an example: the air oxidation of benzene of maleic anhydride
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