Glycinium semi‐malonate and a glutaric acid–glycine cocrystal: new structures with short O—H...O hydrogen bonds

Glycinium semi‐malonate, C₂H₆NO₂⁺·C₃H₃O₄⁻, (I), and glutaric acid–glycine (1/1), C₂H₅NO₂·C₅H₈O₄, (II), are new examples of two‐component crystal structures containing glycine and carboxylic acids. (II) is the first example of a glycine cocrystal which cannot be classified as a salt, as glutaric acid remains completely protonated. In the structure of (I), there are chains formed exclusively by glycinium cations, or exclusively by malonate anions, and these chains are linked with each other. Two types of very short O—H...O hydrogen bonds are present in the structure of (I), one linking glycinium cations with malonate anions, and the other linking malonate anions with each other. In contrast to (I), no direct linkages between molecules of the same type can be found in (II); all the hydrogen‐bonded chains are heteromolecular, with molecules of neutral glutaric acid alternating with glycine zwitterions, linked by two types of short O—H...O hydrogen bonds.     

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 1. Isolated clay nanoplate

The structure and mechanical properties of clay nanoparticles is a subject of growing interest because of their numerous applications in engineering. We present the results of molecular dynamics simulation for a single nanoplate of pyrophyllite - a 2:1 clay mineral consisting of two tetrahedral sheets of SiO4 and an intervening octahedral AlO6 sheet. Simulations were performed in the temperature interval from 5 to 750 K using the ionic-type potentials of Cygan et al. On this basis the temperature dependences of structural parameters, characterizing both tetrahedral and octahedral sheets as well as single lamella, have been studied. Two slightly different structures were observed in this wide temperature interval. The mechanical properties of the nanoplate were calculated from stress-strain diagrams, which have been obtained at relatively slow rates of deformation (for molecular simulations). Using different types of loading, we calculated the full elasticity tensor and estimated the influence of temperature on its components. We estimated also the bending and torsion stiffnesses of the nanoplate as specific characteristics of this type of particle. Because the nanoplate is atomically thin, a reasonable determination of the thickness is a nontrivial problem, both in the modeling of mechanical properties and in physical interpretation of the obtained data. We propose a procedure for its calculation.     

Ruthenium-Catalyzed Hydrogenative Degradation of End-of-Life Poly(lactide) to Produce 1,2-Propanediol as Platform Chemical

The chemical recycling of end-of-life polymers can add some value to a future circular economy. In this regard, the hydrogenative degradation of end-of-life PLA was investigated to produce 1,2-propanediol as product, which is a useful building block in polymer chemistry. In more detail, the commercially available Ru-MACHO-BH complex was applied as catalyst to degrade end-of-life PLA efficiently to 1,2-propanediol under mild conditions. After investigations of the reaction conditions a set of end-of-life PLA goods were subjected to degradation.     

(4+2) Dimerization of imides of arylmaleic acids in the presence of the 3,5-dimethyl-1H-pyrazole and 2,6-lutidine

Imides of arylmaleic acids in the presence of 3,5-dimethyl-1H-pyrazole underwent (4+2) dimerization under heating in chlorobenzene within 24 h to afford 1,2,3,3a,3b,4,5,6,6a,10b-decahydrobenzo[e]pyrrolo[3,4-g]isoindole-1,3,4,6-tetraones in good yields. It was established that during the heating of imides of arylmaleic acid in 2,6-lutidine at 100 °C the (4+2) dimerization products containing a lutidine fragment are obtained.     

Fatty Acid Carboxylate‐ and Anionic Surfactant‐Controlled Delivery Systems That Use Mesoporous Silica Supports

We report the preparation of a MCM‐41 mesoporous material that contains the dye [Ru(bipy)₃]Cl₂ (bipy=bipyridine) inside the mesopores and functionalised with suitable binding groups at the entrance of the pores. Solids S1 – S3 were obtained by the reaction of the mesoporous material with N‐methyl‐N′‐propyltrimethoxysilylimidazolium chloride, N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]thiourea, or N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]urea, respectively. A study of the dye delivery of these systems in buffered water (pH 7.0, 2‐[4‐(2‐hydroxyethyl)piperazin‐1‐yl]ethanesulfonic acid (HEPES), 10^?3 mol dm^?3) in the presence of a family of carboxylate ions was carried out. In the interaction of the anions with the surface of the solids, the response depends on the characteristics of the binding groups (i.e., imidazolium, urea and thiourea) at the pore outlets and their specific interaction with the corresponding anion. The interaction of long‐chain carboxylate ions with the binding sites at the surface of the solids resulted in a remarkable inhibition of the delivery of the dye. This inhibition was observed clearly for the dodecanoate anion, whereas the octanoate, decanoate, cholate, deoxycholate, glycodeoxycholate and taurocholate anions induced a certain pore blockage that varied according to the solid studied. The interaction of smaller anions, such as acetate, butanoate, hexanoate and octanoate, with the solids had no effect on the dye release process. The possible use of the gating system for the chromo‐fluorogenic detection of anionic surfactants through selective dye delivery inhibition was also explored. Molecular dynamic simulations that use force‐field methods have been made to theoretically study the capping carboxylate mechanism. The calculations are in agreement with the experimental results, thus allowing a representation of the dye delivery inhibition in the presence of long‐chain carboxylate ions.     

Synthesis and reactivity of some diselenasila cycles containing an annelated dicarba‐closo‐dodecaborane(12) unit

The use of 1,2‐diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) dianions [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2? prepared in situ as the dilithium salt may lead to irreproducible results. This is shown by the straightforward synthesis of silanes using the purified and isolated dianions, in contrast with previous less successful attempts. Thus, the reactions of the dianions with dichlorosilanes afford the five‐membered diselenasila cycles containing the SiMe₂ or the SiPh₂ units, and with 1,2‐dichloro‐tetramethyldisilane the six‐membered cycle containing the Si₂Me₄ unit. The latter was studied by X‐ray diffraction, and all products were characterized by multinuclear magnetic resonance (¹H, ¹³C, ²⁹Si, ⁷⁷Se NMR) in solution. Novel isotope effects were detected in ¹³C and ⁷⁷Se NMR spectra. Exchange reactions of the five‐ and six‐membered diselanasila cycles with chlorosilanes were studied. Copyright © 2009 John Wiley & Sons, Ltd.     

EPR Study of Ligand Effects in Spin Triads of Bis(o-Semiquinonato)Copper(II) Complexes

We report the X-band (9 GHz) electron paramagnetic resonance (EPR) study of series of bis(o-semiquinonato)copper(II) complexes with different ligands. It was found previously, that exchange interactions in spin triads of these compounds are very sensitive to the structure of the ligand coordinated to the central copper(II) ion. Ligand moderates the copper–radical and radical–radical exchange interactions and strongly changes the magnetic properties of the compound. Depending on a ligand, ferromagnetic or antiferromagnetic character of exchange dominates in the system. The EPR study of these complexes allowed us to obtain information on zero-field splitting parameters and their distributions in the studied compounds. The EPR results compliment previously obtained spectroscopic data on these compounds and suggest the pronounced plasticity of the clusters manifested in the broad distributions of their rhombicity parameters.     

Diversity oriented heterocyclizations of pyruvic acids,aldehydes and 5-amino-<Emphasis Type=Italic>N</Emphasis>-aryl-1<Emphasis Type=Italic>H</Emphasis>-pyrazole-4-carboxamides: catalytic and temperature control of chemoselectivity

Heterocyclization reactions of pyruvic acids, aromatic aldehydes and 5-amino-N-aryl-1H-pyrazole-4-carboxamides yielding four different types of final compounds are described. The reactions involving arylidenpyruvic acids lead with high degree of selectivity to either 4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids or 5-[(2-oxo-2,5-dihydrofuran-3-yl)amino]-1H-pyrazoles, depending on the catalyst type or temperature regime. The interactions based on arylpyruvic acids can take place under kinetic or thermodynamic control producing 7-hydroxy-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine-7-carboxylic acids or 3-hydroxy-1-(1H-pyrazol-5-yl)-1,5-dihydro-2H-pyrrol-2-ones, respectively.