Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport

Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD_7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (P_app) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature.     

Structural verification of a tetrahydrotetrazole compound

Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C₂₅H₃₀N₄O₄, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl₃). A tentative reaction pathway for its dissociation based on ¹H NMR spectral evidence is provided.     

Gas adsorption in mcm-41 porous silicas dynamic measurements using sans

The European Physical Journal E - The isothermal gas adsorption of two hexane isomers (n-hexane and cyclohexane) in the mesopores of MCM-41 silica have been investigated by small angle neutron...     

Ground-state complex formation of perylene with pyromellitic dianhydride studied by static fluorescence quenching

The association of complex formation with static quenching in CT systems was investigated. Evaluation of the data made evident that the inner filter effect must be allowed for. Time-resolved and temperature-dependent stationary measurements of fluorescence led to the separation of dynamic and static quenching components. The static quenching constant is discussed with respect to the equilibrium constant of complex formation determined by absorption spectroscopy.     

Interdiffusion behavior of Hg in HgTe/CdTe superlattices grown on Cd0.96Zn0.04 Te (211)B substrates by molecular beam epitaxy

Double-crystal x-ray rocking curve (DCRC) and secondary-ion mass-spectroscopy (SIMS) measurements have been performed to investigate the effect of rapid thermal annealing on the interdiffusion behavior of Hg in HgTe/CdTe superlattices grown on Cd_0.96Zn_0.04Te (211)B substrates by molecular beam epitaxy. The sharp satellite peaks of the DCRC measurements on a 100-period HgTe/CdTe (100Å/100Å) superlattice show a periodic arrangement of the superlattice with high-quality interfaces. The negative direction of the entropy change obtained from the diffusion coefficients as a function of the reciprocal of the temperature after RTA indicates that the Hg diffusion for the annealed HgTe/CdTe superlattice is caused by an interstitial mechanism. The Cd and the Hg concentration profiles near the annealed HgTe/CdTe superlattice interfaces, as measured by SIMS, show a nonlinear behavior for Hg, originating from the interstitial diffusion mechanism of the Hg composition. These results indicate that a nonlinear interdiffusion behavior is dominant for HgTe/CdTe superlattices annealed at 190°C and that the rectangular shape of HgTe/CdTe superlattices may change to a parabolic shape because of the intermixing of Hg and Cd due to the thermal treatment.     

Control of the block copolymer morphology in templated epoxy thermosets

It has been found that by the addition of low concentrations of an amphiphilic block copolymer to an epoxy resin, novel disordered morphologies can be formed and preserved through curing. This article will focus on characterizing the influence of the block copolymer and casting solvent on the templated morphology achieved in the thermoset sample. The ultimate goal of this work is to determine the parameters that would control the microphase morphology produced. Epoxy resins blended with a series of amphiphilic block copolymers based on hydrogenated polyisoprene (polyethylene-alt-propylene or PEP) and polyethylene oxide (PEO), specifically, were investigated. In this article, the cure-induced order–order phase transition from the spherical to wormlike micelle morphology will also be discussed. It is proposed that the formation of the wormlike micelle structure from the spherical micelle structure is similar to the phase transition behavior that occurs in dilute block copolymer solutions as a function of the influence of the solvent on micelle morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3338–3348, 2007