Arene–perfluoroarene interactions confer enhanced mechanical properties to synthetic nanotubes

Supramolecular nanotubes prepared through macrocycle assembly offer unique properties that stem from their long-range order, structural predictability, and tunable microenvironments. However, assemblies that rely on weak non-covalent interactions often have limited aspect ratios and poor mechanical integrity, which diminish their utility. Here pentagonal imine-linked macrocycles are prepared by condensing a pyridine-containing diamine and either terephthalaldehyde or 2,3,5,6-tetrafluoroterephthalaldehyde. Atomic force microscopy and synchrotron in solvo X-ray diffraction demonstrate that protonation of the pyridine groups drives assembly into high-aspect ratio nanotube assemblies. A 1 : 1 mixture of each macrocycle yielded nanotubes with enhanced crystallinity upon protonation. UV-Vis and fluorescence spectroscopy indicate that nanotubes containing both arene and perfluoroarene subunits display spectroscopic signatures of arene–perfluoroarene interactions. Touch-spun polymeric fibers containing assembled nanotubes prepared from the perhydro- or perfluorinated macrocycles exhibited Young''s moduli of 1.09 and 0.49 GPa, respectively. Fibers containing nanotube assemblies reinforced by arene–perfluoroarene interactions yielded a 93% increase in the Young''s modulus over the perhydro derivative, up to 2.1 GPa. These findings demonstrate that tuning the chemical composition of the monomeric macrocycles can have profound effects on the mechanical strength of the resulting assemblies. More broadly, these results will inspire future studies into tuning orthogonal non-covalent interactions between macrocycles to yield nanotubes with emergent functions and technological potential.

Arene–perfluoroarene interactions resulted in enhanced crystallinity between analogous perhydro- and perfluoro macrocycles in a supramolecular nanotube assembly.     

Optically active cyclic hexapeptides with covalently attached pyrene probes: selective alkaline earth metal ion recognition using excimer emission

[structure: see text] The synthesis of two optically active pyrene-modified cyclic hexapetides and their selectivity toward the complexation of alkaline earth metal ions are reported. Complexation was studied by optical and chiroptical methods. The cyclic peptides are forming 2:1 sandwich complexes with the metal ions.     

Tonks-Langmuir problem for a bi-Maxwellian plasma

An analytical solution of the Tonks-Langmuir (TL) problem with a bi-Maxwellian electron energy distribution function (EEDF) is obtained for a plasma slab. The solution shows that the ambipolar potential, the plasma density distribution, and the ion flux to the wall are mainly governed by the cold electrons, while the ionization rate and voltage drop across the wall sheath are governed by the hot electrons. The ionization rate by direct electron impact is found to be spatially rather uniform, contrary to the T-L solution where it is proportional to the plasma density distribution. The temperature of hot electrons defined by the ionization balance is found to be close to that of the T-L solution for a mono-Maxwellian EEDF, and is in reasonable agreement with experiments carried out in a low pressure capacitance RF discharge. The energy balance for cold electrons in this discharge shows that their heating by hot electrons via Coulomb interaction is equalized by the cold electrons' escape to the RF electrodes during collapse of the RF sheath     

Distribution of metastable argon atoms in the modified Grimm-type electrical discharge

The absorbance by metastable argon atoms of the Ar 696.543 nm line in the modified Grimm-type electrical discharge source was measured at different discharge conditions and at distances varying from 0.25 to 6 mm from the cathode. A uranium/argon hollow cathode lamp was used as primary source, which gave an argon gas temperature of 850 K when run at 12 mA. A maximum absorbance of 0.57 was found 3 mm from the cathode at 600 V, 80 mA. The magnitude of absorbance increases with discharge current while the position of maximum absorbance shifts away from the cathode with increase in discharge voltage. The quenching of metastable atoms by nitrogen is demonstrated.The spatial distribution of the intensity of four different types of spectral lines is shown. The approximate number densities of the different particles are 10¹²cm^?3 for metastable argon atoms, 10¹⁶cm^?3 for neutral argon atoms, 10¹³ cm^?3 for sputtered copper atoms and 10¹⁴cm^?3for electrons.     

Light clusters in nuclear matter of finite temperature

We investigate properties and the distribution of light nuclei ( ) in symmetric nuclear matter of finite temperature within a microscopic framework. For this purpose we have solved few-body Alt-Grassberger-Sandhas-type equations for quasi-nucleons that include self-energy corrections and Pauli blocking in a systematic way. In a statistical model we find a significant influence in the composition of nuclear matter if medium effects are included in the microscopic calculation of nuclei. If multiplicities are frozen out at a certain time (or volume), we expect significant consequences for the formation of light fragments in a heavy ion collision. As a consequence of the systematic inclusion of medium effects, the ordering of multiplicities becomes opposite to the law-of-mass action of ideal components. This is necessary to explain the large abundance of -particles in a heavy ion collision that are otherwise largely suppressed in an ideal equilibrium scenario.PACS: 25.70.-z Low and intermediate energy heavy-ion reactions - 25.70.Pq Multifragment emission and correlations - 21.65. + f Nuclear matter - 21.45. + v Few-body systems     

Solvent-mediated self-association of a Horning-crown macrocycle

A member of a new class of novel macrocycles possessing both polyether and phenolic functionalities, forms dimers in both the solid-state and in solution when exposed to chloroform, dichloromethane or toluene, but does not self-associate in the presence of dimethyl sulfoxide.     

Direct preparation of monoarylidene derivatives of aldehydes and enolizable ketones with DIMCARB

[reaction: see text] Aryl alpha,beta-unsaturated ketones and aldehydes were synthesized, in moderate to excellent yields, with use of dimethylammonium dimethyl carbamate (DIMCARB) as a recyclable reaction medium and as a catalyst.