On the pressure correction of capillary melt rheology data

In this paper, the importance of a pressure correction of viscosity data obtained in capillary melt rheology is demonstrated. A linear polycarbonate has been chosen as a highly pressure-sensitive material for which data obtained by rotational rheometry does not overlap with capillary data. This apparent problem with the Cox–Merz relation is attributed to the existence of a mean pressure inside the capillary which is significantly different from atmospheric conditions. Different methods to determine the pressure coefficient of polycarbonate have been evaluated based on experiments performed with a capillary rheometer equipped with a pressure chamber. It is demonstrated that the pressure coefficient obtained at constant shear stress and the pressure coefficient obtained by the superposition method represent accurate pressure coefficient values. Two approaches are proposed to correct the original capillary data. In the direct methodology, the pressure coefficient is used to rescale the mean pressure inside the capillary to atmospheric conditions. The indirect approach consists of first constructing a mastercurve at a certain reference pressure using capillary data obtained with a pressure chamber. The resulting mastercurve can then be rescaled to atmospheric conditions. It is shown that both methods lead to viscosity curves on which both rotational and capillary data overlap, hence confirming the Cox–Merz relationship for polycarbonate. The indirect method is proven to be advantageous since it opens the possibility to significantly extend the shear rate window in which viscosities can be measured.     

Persistent metal bis(hexafluoroacetylacetonato) complexes featuring a 2,2'-bipyridine substituted triarylamminium radical cation

Herein, we describe the preparation of a 2,2'-bipyridine derivative containing a redox-active N,N'-(4,4'-dimethoxydiphenylamino) substituent (1), which readily coordinates M(hfac)(2) salts [M = Mn (2), Ni (3), Cu (4)] to generate stable, neutral, and pseudo-octahedral coordination complexes, which have been fully characterized. Cyclic voltammetry and spectroelectrochemical measurements on complexes 2-4 indicate stable one-electron oxidation processes, and the formation of persistent radical cation complexes. The neutral complexes (M = Mn or Ni) were subject to one-electron oxidation with NOPF(6) in acetonitrile, and magnetic moments of the resulting solutions were obtained using the Evans method at different temperatures. Our experimental results suggest that the first reported ferromagnetically coupled metal-triarylamminum radical cation complex is obtained when M = Mn(2+), and antiferromagnetic coupling results when M = Ni(2+). These results are supported by results from density functional theory calculations, which indicate that a π spin polarization mechanism for magnetic exchange coupling is operative in singly oxidized complexes, 2-4.     

Mid‐IR Spectroscopy and Structural Features of Protonated Carbonic Acid in the Gas Phase

An anti trihydroxycarbenium ion is revealed to be the gas‐phase structure of protonated carbonic acid by IR multiple‐photon dissociation spectroscopy (see picture for calculated structure and comparison of experimental and computed spectra). Deprotonation yields anti‐H₂CO₃ with a nominal gas‐phase basicity of 724 kJ mol^?1.

     

Use of hydrogen/deuterium exchange mass spectrometry and mutagenesis as a tool to identify the binding region of inhibitors targeting the human mitotic kinesin Eg5

An experimental procedure associating both hydrogen/deuterium exchange mass spectrometry (H/D-MS) and mutagenesis was developed to identify the protein-binding region of small inhibitors targeting the motor domain of the human mitotic kinesin Eg5. All the tested inhibitors decrease the deuterium incorporation rate of the same peptides corresponding to the following secondary structure elements: loop L5/helix alpha2 (region Tyr125-Glu145) and strand beta5/helix alpha3 (region Ile202-Leu227). Replacement of these two regions by the equivalent ones from N. crassa conventional kinesin heavy chain completely abolishes the modification of the deuterium incorporation rate by the inhibitors as well as their effects on the basal ATPase activity. The six tested inhibitors thus share a common binding site on Eg5. The strategy reported here allows the regions of a protein involved in ligand binding to be rapidly pinpointed and can be applied to other proteins and used as a general in vitro screening procedure to identify compounds targeting specific binding regions.     

IR spectroscopic features of gaseous C7H7O+ ions: benzylium versus tropylium ion structures

Gaseous [C7H7O]+ ions have been formed by protonation of benzaldehyde or tropone (2,4,6-cycloheptatrienone) in the cell of an FT-ICR mass spectrometer using C2H5(+) as a Br?nsted acid. The so-formed species have been assayed by infrared multiphoton dissociation (IRMPD) using the free electron laser (FEL) at the CLIO (Centre Laser Infrarouge Orsay) facility. The IRMPD features are quite distinct for ions from the two different precursors, pointing to two different isomers. A number of potential structures for [C7H7O]+ ions have been optimized at the B3LYP/6-31+G(d,p) level of theory, and their relative energies and IR spectra are reported. On this basis, the IRMPD spectra of [C7H7O]+ ions are found to display features characteristic of O-protonated species, with no evidence of any further skeletal rearrangements. The so-formed ions are thus hydroxy-substituted benzylium and tropylium ions, respectively, representative members of the benzylium/tropylium ion family. The IRMPD assay using the FEL laser light has allowed their unambiguous discrimination where other mass spectrometric techniques have yielded a less conclusive answer.     

DC conductivity of a suspension of insulating particles with internal rotation

We analyse the consequences of Quincke rotation on the conductivity of a suspension. Quincke rotation refers to the spontaneous rotation of insulating particles dispersed in a slightly conducting liquid and subject to a high DC electric field: above a critical field, each particle rotates continuously around itself with an axis pointing in any direction perpendicular to the DC field. When the suspension is subject to an electric field lower than the threshold one, the presence of insulating particles in the host liquid decreases the bulk conductivity since the particles form obstacles to ion migration. But for electric fields higher than the critical one, the particles rotate and facilitate ion migration: the effective conductivity of the suspension is increased. We provide a theoretical analysis of the impact of Quincke rotation on the apparent conductivity of a suspension and we present experimental results obtained with a suspension of PMMA particles dispersed in weakly conducting liquids.     

Pseudo-coefficients des séries <Emphasis Type=Italic>κ</Emphasis>-discrètes de GL(<Emphasis Type=Italic>n,F</Emphasis>)

Let F be a non-Archimedean locally compact field, n be an integer ≥ 2, κ be a character of F ^× of finite order dividing n, and G be the group GL(n, F). We prove that if π is an irreducible κ-discrete series of G, then there exist some pseudo-coefficients for the twisted character trace(π ∘ A) where A denotes a non-zero intertwining operator between π ⊗ (κ ∘ det) and π.     

Short synthesis of new salacinol analogues and their evaluation as glycosidase inhibitors

Versatile synthesis of some analogues of the naturally-occurring α-glucosidase inhibitor salacinol (1), involving thioanhydro alditol moieties with erythro, d,l-threo, xylo, ribo, d-arabino and d-manno configurations is described. Nucleophilic attack at the least-hindered carbon atom of an l- or d-protected erythritol cyclic sulfate by the thioanhydro alditol sulfur atom yielded the desired zwitterionic compounds. In addition, the preparation of the cyclic sulfates of 2,4-O-benzylidene-d-erythritol and 2,4-O-isopropylidene-l-erythritol was improved. Enzyme inhibition tests showed that most of the new compounds were weak but specific inhibitors, while good inhibitory activity was found for a six-membered ring analogue (β-glucosidase: K_i=16 μM).