Reductive desorption of thiolate from monolayer protected gold clusters

The "electrochemical potential window" of monolayer-protected gold cluster (MPC) nanoelectrodes is probed where the electrified liquid-liquid interface is used as the detector. The first observation of the reductive desorption of thiolate at negative MPC core charge is reported.     

Viscosity and dynamics of nanorod (carbon nanotubes, cellulose whiskers, stiff polymers and polymer fibers) suspensions

The zero shear viscosity and the dynamic behaviors of different nanorod dispersions (carbon nanotubes (CNTs), cellulose whiskers, polymer nanofibers, crosslinked polymer nanofibers, and stiff polymers such as poly(γ-benzyl-α-l-glutamate) (PBLG)) were compared and discussed from literature data. Their Brownian dynamic behaviors have always been discussed in the frame of the Doi–Edwards theory. In agreement with this theory, the straight rigid rods (CNTs, cellulose whisker, polymer nanofibers) obey a master curve in the reduced viscosity (or rotary diffusivity) c power laws on viscosity (η ₀ ∝ φ ³) and diffusivity (D _r ∝ ? ^?2). On the contrary, stiff polymer chains and crosslinked polymer fibers at temperature above T _g exhibit different and two distinct dynamic behaviors. Despite their deviation from the ideal rigidity, surprisingly it can be noted that stiff polymers such as PBLG have been extremely used in the literature to verify the Doi–Edwards theory. Finally, flexible crosslinked chains at T > T _g , do not obey the Doi–Edwards theory, and their dynamics are close to the physics of polymer solutions in terms of power laws.     

Developing shift problems to foster geometrical proof and understanding

Meaningful learning of formal mathematics in regular classrooms remains a problem in mathematics education. Research shows that instructional approaches in which students work collaboratively on tasks that are tailored to problem solving and reflection can improve students’ learning in experimental classrooms. However, these sequences involve often carefully constructed reinvention route, which do not fit the needs of teachers and students working from conventional curriculum materials. To help to narrow this gap, we developed an intervention—‘shift problem lessons’. The aim of this article is to discuss the design of shift problems and to analyze learning processes occurring when students are working on the tasks. Specifically, we discuss three paradigmatic episodes based on data from a teaching experiment in geometrical proof. The episodes show that is possible to create a micro-learning ecology where regular students are seriously involved in mathematical discussions, ground their mathematical understanding and strengthen their relational framework.     

Three 5H‐indeno­[1,2‐c]­pyridazin‐5‐one derivatives,potent type‐B mono­amine oxidase inhibitors

The structures of three compounds, namely 7‐methoxy‐2‐[3‐(tri­fluoro­methyl)­phenyl]‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₉H₁₁F₃N₂O₂, (Id), 6‐methoxy‐2‐[3‐(tri­fluoro­methyl)­phenyl]‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₉H₁₁F₃N₂O₂, (IId), and 2‐methyl‐6‐(4,4,4‐tri­fluoro­butoxy)‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₆H₁₃F₃N₂O₂, (IIf), which are potent reversible type‐B mono­amine oxidase (MAO‐B) inhibitors, are presented and discussed. Compounds (Id) and (IId) crystallize in a nearly planar conformation. The crystal structures are stabilized by weak C—H⋯O hydrogen bonds. The packing is dominated by π–π stacking interactions between the heterocyclic central moieties of centrosymmetrically related mol­ecules. In compound (IIf), the tri­fluoro­ethyl termination is almost perpendicular to the plane of the ring.     

The obstacle problem for shallow shells in curvilinear coordinates

Starting from the 3D Signorini problem in presence of a plane obstacle, we justify the limit inequation of unilateral contact posed in a 2D domain. In particular, we show that we can uncouple the three covariant components of the limit Kirchhoff–Love displacement field so that the non-penetrability condition involves only the “transverse” component as this is the case in Cartesian framework.     

Foldable Detergents for Membrane Protein Study: Importance of Detergent Core Flexibility in Protein Stabilization

Membrane proteins are of biological and pharmaceutical significance. However, their structural study is extremely challenging mainly due to the fact that only a small number of chemical tools are suitable for stabilizing membrane proteins in solution. Detergents are widely used in membrane protein study, but conventional detergents are generally poor at stabilizing challenging membrane proteins such as G protein-coupled receptors and protein complexes. In the current study, we prepared tandem triazine-based maltosides (TZMs) with two amphiphilic triazine units connected by different diamine linkers, hydrazine (TZM−Hs) and 1,2-ethylenediamine (TZM−Es). These TZMs were consistently superior to a gold standard detergent (DDM) in terms of stabilizing a few membrane proteins. In addition, the TZM−Es containing a long linker showed more general protein stabilization efficacy with multiple membrane proteins than the TZM−Hs containing a short linker. This result indicates that introduction of the flexible1,2-ethylenediamine linker between two rigid triazine rings enables the TZM−Es to fold into favourable conformations in order to promote membrane protein stability. The novel concept of detergent foldability introduced in the current study has potential in rational detergent design and membrane protein applications.     

Combinatorics of Free Cumulants

We derive a formula for expressing free cumulants whose entries are products of random variables in terms of the lattice structure of non-crossing partitions. We show the usefulness of that result by giving direct and conceptually simple proofs for a lot of results about R-diagonal elements. Our investigations do not assume the trace property for the considered linear functionals.