Amplification of changes of a thin film's macromolecular structure into macroscopic reaction-diffusion patterns

A reaction-diffusion process induced from a micronetwork geometry amplifies changes in the molecular structure of a thin gel film into macroscopic readout patterns. When the gel undergoes a helix-to-coil phase transition, the patterns formed by RD switch from symmetry-broken to symmetric ones. Theoretical analysis explains how the system reconfigures internally in response to mass transfer between the applied network and the probed film.     

Synthesis of a cisplatin derivative from lithocholic acid

A new steroidal-platinum(II) hybrid compound was synthesized using a simple and efficient methodology. The synthesis was performed by a convergent approach with cross metathesis (CM) as a key step. An olefin derived from lithocholic acid and a vinyl substituted ethylenediamine derived from l-serine were used as chiral building blocks, which were combined in the CM step. The most important advantage of this method was the utilization of l-serine as a cheap, stereoisomerically pure substrate. A steroid with a diamino system in the side chain was subjected to reaction with potassium tetrachloroplatinate to obtain the target platinum(II) complex. Attempts to synthesize similar diamine systems using the asymmetric Strecker reaction were unsuccessful.     

Does a fluorinated Lewis acid catalyst change the molecular mechanism of the decomposition process of nitroethyl carboxylates?

The molecular mechanism of the decomposition reaction of nitroethyl benzoates catalyzed by Lewis acids based on boron element—BH₃ and BF₃—was studied using density functional theory methods. These reactions take place much faster than the uncatalyzed process. However, the presence of fluorinated Lewis acids has a unique influence on the molecular mechanism. In the case of BF₃, a change from a one-step mechanism to a two-step one involving a zwitterionic intermediate is observed.     

Electrochemical properties of positive electrode in lead-acid battery modified by ammonium-based ionic liquids

The influence of selected types of ammonium ionic liquid (AIL) additives on corrosion and functional parameters of lead-acid battery positive electrode was examined. AILs with a bisulfate anion used in the experiments were classified as protic, aprotic, monomeric, and polymeric, based on the structure of their cation. Working electrodes consisted of a lead-calcium-tin alloy utilized in the industry for manufacturing current collectors of positive electrodes in lead-acid batteries (LABs). This alloy was used in the first part of the study for the evaluation of corrosion intensity and stability of electrolyte with AIL additives. In the second part, the grid made of the examined alloy was covered with positive active mass, the composition of which was modified by selected AIL. The selection of an appropriate substance was made based on parameters such as corrosion potential, corrosion current, polarization resistance, and hydrogen and oxygen evolution potentials. Techniques such as linear sweep voltammetry, corrosimetry, and electrochemical impedance spectroscopy were used. The conducted measurements revealed that polymeric AIL additive had an exceptionally positive influence on the inhibition of the corrosion process in LAB and electrochemical window of the electrolyte. The influence of this compound on the specific capacity and resistance of the active mass was also discussed.

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Discovery and Enumeration of Organic‐Chemical and Biomimetic Reaction Cycles within the Network of Chemistry

Analysis of the chemical‐organic knowledge represented as a giant network reveals that it contains millions of reaction sequences closing into cycles. Without realizing it, independent chemists working at different times have jointly created examples of cyclic sequences that allow for the recovery of useful reagents and for the autoamplification of synthetically important molecules, those that mimic biological cycles, and those that can be operated one‐pot.     

Easy and Safe preparations of (diacetoxyiodo) arenes from iodoarenes, with urea-hydrogen peroxide adduct (UHP) as the oxidant and the fully interpreted (1)H- and (13)C-NMR spectra of the products

An easy and safe, though only moderately effective method is presented for preparing (diacetoxyiodo)arenes, ArI(OAc)2, from iodoarenes, ArI, using the commercially available and easily handled urea-hydrogen peroxide adduct (UHP) as the oxidant. The reactions take place in anhydrous AcOH/Ac2O/AcONa (a catalyst)mixtures, at 40 oC for 3.5 h to afford the purified ArI(OAc)2 in 37-78% yields. The fully interpreted (1)H- and (13)C-NMR spectra of the ArI(OAc)2 products are reported.     

Angular Overlap Studies of Mono-(Aminodiphosphonato)Copper(II) Complexes in Aqueous Solutions

Electronic absorption spectra of copper(II) complexes with iminodimethylenephosphonates R-N(CH₂PO₃H₂)₂ type (L, R-dmp), in aqueous solution have been characterized and quantitatively interpreted. The geometry of species in aqueous solution at pH 7–8 has been assumed on the basis of our previous combination of UV spectrophotometric measurements and ESR spectra, as well as data obtained from potentiometric titration. The ligand-field spectra (d–d transitions) of the [CuL(H₂O)_x]^2– chromophores (where x = 2, 3) have been treated by the angular overlap model (AOM) and C _2v symmetry. Low-symmetry splittings of the broad asymmetric bands in the spectra of solutions at room temperature were resolved by Gaussian analysis. The effect of the and bonding of the tridentate (and tetradentate) ligands (with oxygen-donor and nitrogen-donor ligators) on the central metal ion has been described in the ligand-field framework.