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.     

Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions

A new approach has been developed to improve SO₂ sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO₂ capture. The interaction between these cyano‐containing ILs and SO₂ was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO₂ capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO₂ was easy to release by heating or bubbling N₂ through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO₂ capture.     

Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Tips and Tricks for the Surface Engineering of Well-Ordered Morphologically Driven Silver-Based Nanomaterials

Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted.     

Excited-State Dynamics of Non-Luminescent and Luminescent π-Radicals

Recently, the potential use of organic π-radicals and related spin systems has been expanded to modern technological applications. The unique excited-state dynamics of organic π-radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up-conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π-radicals have been recently reported, which are especially interesting for application in organic light-emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited-state nature of stable π-radicals as well as the control of their excited-state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited-state dynamics of both photostable non(weakly)-luminescent and luminescent π-radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high-spin photoexcited states and control of the excited-state dynamics by using non-luminescent π-radicals, 2) unique excited-state dynamics of luminescent π-radicals and radical excimers, and 3) applications utilizing excited-state dynamics of π-radicals.