Two-phase channel structures based on alpha-cyclodextrin-polyethylene glycol inclusion complexes

Wide-angle X-ray scattering observations of alpha-cyclodextrin (CD)-poly(ethylene glycol) (PEG) inclusion complexes (ICs) have shown for the first time that two crystalline columnar modifications (forms I and II) are produced in the process of their formation. This was made possible by precise azimuthal X-ray diffraction scanning of oriented IC samples. Form I is characterized by CDs threaded onto PEG chains and arranged along channels in the order head-to-head/tail-to-tail, while form II is formed by unbound CDs also arranged into columns in a head-to-tail and also possibly a head-to-head/tail-to-tail manner, probably as a result of template crystallization on the form I IC crystals. It was shown that similar structural peculiarities are inherent for channel structures based on ICs obtained with PEG with a wide range of molecular weights (MWs). The characteristic feature of ICs based on PEG, especially with MW > 8000, is the presence of unbound polymer in the composition of the complex. The amount of unbound PEG was shown to rise with increasing MW of PEG, resulting in greater imperfections in the IC crystalline structure. The polyblock structure of ICs based on alpha-CD and PEG was therefore proposed.     

Accurate intermolecular ground state potential of the Ar-N2 van der Waals complex

After carrying out a systematic basis set convergence study, we evaluate several ground state potential energy surfaces of the Ar-N(2) van der Waals complex at the coupled cluster singles and doubles model including connected triples corrections. We use the aug-cc-pVXZ (X=5,Q,D) and the daug-cc-pVQZ basis sets augmented with a set of 3s3p2d1f1g (denoted 33211) and 3s3p2d2f1g (denoted 33221) midbond functions, respectively. aug-cc-pVTZ-33211 results were available in the literature. The aug-cc-pV5Z-33211 (daug-cc-pVQZ-33221) surface is characterized by a T-shaped minimum at R(e)=3.709 (3.701) A and of 99.01 (102.50) cm(-1), and a linear saddle point at 4.260 (4.257) A and D(e)=75.28 (79.73) cm(-1). These results are compared with the values provided by the semiempirical potentials available, and those of previous theoretical studies. The basis set convergence of the intermolecular potentials is also analyzed. From the potentials the rovibronic spectroscopic properties are determined. We study the basis set convergence of the rotational frequencies. The binding parameters that characterized the aug-cc-pVTZ-33211 surface are reasonable, but the surface is not good enough to evaluate the microwave spectra. The aug-cc-pVQZ-33211 basis set results considerably improve the triple zeta and are close to the aug-cc-pV5Z-33211. Considering the small differences between the quadruple and the quintuple zeta surfaces, the latter results can be expected to be close to convergence. At this level the differences with respect to the accurate experimental frequencies are in the order of 0.7%. In the case of the daug-cc-pVXZ-33211,33221 (X=5,Q,T,D) series, the convergence of the interaction energies with respect to basis set improvement is not so smooth. The errors in the frequencies obtained with the daug-cc-pVQZ-33221 basis set with respect to experiment are in the order of 0.4%.     

Free-radical selective functionalization of 1,4-naphthoquinones by perfluorodiacyl peroxides

Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity.     

A New Cells‐Compatible Microfluidic Device for Single Channel Recordings

We report the fabrication of a microfluidic apparatus and the realization of a sensors based on PEDOT : PSS, a biocompatible semiconductor polymer used in substitution of standard electrodes for electrophysiological studies and for detection of nanopores in membrane. This gives the possibility to study the mechanisms of ions balance and molecular transport though cell membranes. In particular the apparatus is based on two chambers connected through an aperture in a PTFE sheet where lipid bilayer are formed using Montal‐Mueller method, and the pore‐forming proteins activity is detected by polymeric electrodes. This methodology could be applied to examine different membrane proteins for the purpose of biosensing, drug screening and nanopore technologies.     

Zn2+‐Regulated Self‐Sorting and Mixing of Phosphates and Carboxylates on the Surface of Functionalized Gold Nanoparticles

Herein, we describe the self‐sorting of phosphate‐ and carboxylate‐containing molecules on the surface of monolayer‐protected gold nanoparticles. Self‐sorting is driven by selective interactions between the phosphate probe and Zn²⁺ complexes in one monolayer; these interactions force the carboxylate probe to move to a second type of nanoparticle. This process effectively separates the probes and causes their localization in well‐defined spaces surrounding the nanoparticles. The removal/addition of Zn²⁺ metal ions from the system is used to convert the system from an ordered to a disordered state and vice versa. The possibility to control the location and transport of populations of molecules in a complex mixture creates new perspectives for the development of innovative complex catalytic systems that mimic nature.     

The Synthesis of Some Fused Pyrazolo‐1,4‐Naphthoquinones

New fused pyrazolo‐1,4‐naphthoquinones were prepared from the reaction of hydrazines with 6‐(4‐methyl‐3‐pentenyl)‐1,4‐naphthoquinone. The reaction was extended to hydroxylamine to afford the corresponding isoxazolo‐1,4‐napthoquinone compound.     

Hydrogen bonding-based 3D supramolecular architecture of [Cu(CHA)2][TCM]·11H2O

Reaction of Na₄TCM (1) (H₄TCM = tetra[4-(carboxyphenyl)oxamethyl]methane) with [Cu(CHA)](ClO₄)₂ (2)(CHA = 1,3,6,8,11,14-hexaaz atricyclo[12.2.1.1.^8,11] octadecane) in a DMF-water mixture yields [Cu(CHA)]₂[TCM] (3). Structural analysis of [Cu(CHA)]₂[TCM]·11H₂O (3·11H₂O) by single crystal X-ray diffraction reveals strong copper-oxygen bonds between two complex cations and the tetraanion leading to a 3D coordination network (zwitterionic structure), consolidated through additional NH...O=C hydrogen bonding within the cation/anion association. The resulting coordination geometry around a copper atom is a distorted square pyramidal with an oxygen atom of the anionic ligand in the apical position. A 3D supramolecular network is developed in the crystal based only on NH...OC hydrogen bonds between the macrocyclic metallic tecton and the carboxylate groups of neighboring 3D coordinated (zwitterionic) moieties. The pseudotetrahedral TCM^4? tetraanionic ligand induces a diamondoid architecture formed of large distorted adamantanoid cages.