Molecular structure of 3-phenyl-5-methyl-4-isoxazolyl-penicillin sulfone (oxacillin sulfone): C19H19N3O8S

The crystal structure of oxacillin sulfone has been determined by single-crystal X-ray diffraction techniques and refined by full-matrix least squares. The penicillin molecule cocrystallizes with H₂O in an orthorhombic space groupP2₁2₁2₁ witha=10.303(7) Å,b=26.735(17) Å, andc=7.384(4) Å. The calculated density is 1.526 g cm^–3, with aZ value of 4. FinalR-factor is 0.035. The oxidation of the sulfur atom is discussed in terms ofS1 conformation of the penam moiety and in terms of hydrogen-bond formation between one oxygen of the sulfur atom and the amidic hydrogen of the C₆ side-chain. A comparison with oxacillin and cloxacillin sulfoxide is also made.     

Enzymatic resolution of substituted mandelic acids

A series of substituted mandelic acids were prepared and subjected to enzymatic resolution utilizing Lipase PS ‘Amano’.     

Combining UV photodissociation with electron transfer for peptide structure analysis

The combination of near‐UV photodissociation with electron transfer and collisional activation provides a new tool for structure investigation of isolated peptide ions and reactive intermediates. Two new types of pulse experiments are reported. In the first one called UV/Vis photodissociation–electron transfer dissociation (UVPD‐ETD), diazirine‐labeled peptide ions are shown to undergo photodissociation in the gas phase to form new covalent bonds, guided by the ion conformation, and the products are analyzed by electron transfer dissociation. In the second experiment, called ETD‐UVPD wherein synthetic labels are not necessary, electron transfer forms new cation–peptide radical chromophores that absorb at 355 nm and undergo specific backbone photodissociation reactions. The new method is applied to distinguish isomeric ions produced by ETD of arginine containing peptides. Copyright © 2015 John Wiley & Sons, Ltd.     

Gas‐Separation Membranes Loaded with Porous Aromatic Frameworks that Improve with Age

Porosity loss, also known as physical aging, in glassy polymers hampers their long term use in gas separations. Unprecedented interactions of porous aromatic frameworks (PAFs) with these polymers offer the potential to control and exploit physical aging for drastically enhanced separation efficiency. PAF‐1 is used in the archetypal polymer of intrinsic microporosity (PIM), PIM‐1, to achieve three significant outcomes. 1) hydrogen permeability is drastically enhanced by 375 % to 5500 Barrer. 2) Physical aging is controlled causing the selectivity for H₂ over N₂ to increase from 4.5 to 13 over 400 days of aging. 3) The improvement with age of the membrane is exploited to recover up to 98 % of H₂ from gas mixtures with N₂. This process is critical for the use of ammonia as a H₂ storage medium. The tethering of polymer side chains within PAF‐1 pores is responsible for maintaining H₂ transport pathways, whilst the larger N₂ pathways gradually collapse.     

On the hydrogen atom beyond the Born–Oppenheimer approximation

Recently a new formulation of quantum mechanics has been suggested which is based on the concept of signed particles, that is, classical objects provided with a position, a momentum and a sign simultaneously. In this article, we comment on the plausibility of simulating atomic systems beyond the Born–Oppenheimer approximation by means of the signed particle formulation of quantum mechanics. First, to show the new perspective offered by this new formalism, we provide an example studying quantum tunnelling through a simple Gaussian barrier in terms of the signed particle formulation. Then, we perform a direct simulation of the hydrogen atom as a full quantum two‐body system, showing that the formalism can be a very promising tool for first‐principle‐only quantum chemistry.     

Eight new crystal structures of 5‐(hydroxymethyl)uracil, 5‐carboxyuracil and 5‐carboxy‐2‐thiouracil: insights into the hydrogen‐bonded networks and the predominant conformations of the C5‐bound residues

In order to examine the preferred hydrogen‐bonding pattern of various uracil derivatives, namely 5‐(hydroxymethyl)uracil, 5‐carboxyuracil and 5‐carboxy‐2‐thiouracil, and for a conformational study, crystallization experiments yielded eight different structures: 5‐(hydroxymethyl)uracil, C₅H₆N₂O₃, (I), 5‐carboxyuracil–N,N‐dimethylformamide (1/1), C₅H₄N₂O₄·C₃H₇NO, (II), 5‐carboxyuracil–dimethyl sulfoxide (1/1), C₅H₄N₂O₄·C₂H₆OS, (III), 5‐carboxyuracil–N,N‐dimethylacetamide (1/1), C₅H₄N₂O₄·C₄H₉NO, (IV), 5‐carboxy‐2‐thiouracil–N,N‐dimethylformamide (1/1), C₅H₄N₂O₃S·C₃H₇NO, (V), 5‐carboxy‐2‐thiouracil–dimethyl sulfoxide (1/1), C₅H₄N₂O₃S·C₂H₆OS, (VI), 5‐carboxy‐2‐thiouracil–1,4‐dioxane (2/3), 2C₅H₄N₂O₃S·3C₆H₁₂O₃, (VII), and 5‐carboxy‐2‐thiouracil, C₁₀H₈N₄O₆S₂, (VIII). While the six solvated structures, i.e. (II)–(VII), contain intramolecular S(6) O—H…O hydrogen‐bond motifs between the carboxy and carbonyl groups, the usually favoured R₂²(8) pattern between two carboxy groups is formed in the solvent‐free structure, i.e. (VIII). Further R₂²(8) hydrogen‐bond motifs involving either two N—H…O or two N—H…S hydrogen bonds were observed in three crystal structures, namely (I), (IV) and (VIII). In all eight structures, the residue at the ring 5‐position shows a coplanar arrangement with respect to the pyrimidine ring which is in agreement with a search of the Cambridge Structural Database for six‐membered cyclic compounds containing a carboxy group. The search confirmed that coplanarity between the carboxy group and the cyclic residue is strongly favoured.     

Katalysatoren für die Produktion von Biokunststoffen

Bioplastics represent an important possibility to reduce environmental pollution by non‐degradable plastics and open up new resources for plastics production. To promote wide application of bioplastics, new catalysts are urgently needed. This article summarises recent developments of robust lactide polymerisation catalysts as well as the embedding of the produced PLA into the life cycle of bioplastics.     

Thermal and colour properties of leuco dye-based thermochromic composite with dodecanol solvent

Leuco dye–developer–solvent composites with thermochromic properties were studied. The applied 1-dodecanol solvent shows β crystalline, α solid (rotator) and liquid phases. The inclusion of the crystal violet lactone dye increases transition temperatures of all phases and strengthens the α phase. The benzyl 4-hydroxybenzoate developer causes opposite effects and prevents the appearance of the α phase. These consequences combine in ternary composites, where lower transition temperatures were obtained as in the solvent, but the α phase is formed more likely as expected due to the presence of the developer. The hydration of the composite strengthens its crystalline network, but makes α phase more unstable. The thermal properties were related to the temperature-dependent colour. Composites with well-resolved α and β phases at cooling show a typical colour hysteresis. If only weak α phase or none at all was found in DSC curves, the colour hysteresis has an unusual shape with heating and cooling curves crossing each other. The hydration of the composite changes the colorimetric properties in accordance with the relation found for anhydrous composite. More conclusions and interrelations between the two properties require application of other analytical methods.     

Factors Governing the Formation of Oxygen-Containing Copper Powders in a Plasma-Solution System

Plasma Chemistry and Plasma Processing - The formation of precipitation under the action of a direct current atmospheric pressure discharge in air on a copper (II) nitrate solution was...