Ein Trityläther des Glykogens

Ohne Zusammenfassung     

Über ein allgemein verwendbares Verfahren der Dampfdichtebestimmung unter beliebigem Drucke

Ohne Zusammenfassung     

Severi varieties on blow-ups of the symmetric square of an elliptic curve

We prove that certain Severi varieties of nodal curves of positive genus on general blow-ups of the twofold symmetric product of a general elliptic curve are nonempty and smooth of the expected dimension. This result, besides its intrinsic value, is an important preliminary step for the proof of nonemptiness of Severi varieties on general Enriques surfaces.     

Conformational and electronic consequences in crafting extended, π-conjugated, light-harvesting macrocycles

The synthesis of a new series of free‐base, Ni^II and Zn^II 2,3,12,13‐tetra(ethynyl)‐5,10,15,20‐tetraphenyl porphyrins is described. Upon heating, two of the four ethynyl moieties undergo Bergman cyclization to afford the monocyclized 2,3‐diethynyl‐5,20‐diphenylpiceno[10,11,12,13,14,15‐jklmn]porphyrin in 30 %, 10 %, and trace yields, respectively. The structures of all products were investigated by using quantum chemical calculations and the free‐base analogue was isolated and crystallized; all compounds show significant deviation from the idealized planar structure. No fully‐cyclized bispiceno[20,1,2,3,4,5,10,11,12,13,14,15‐fghij]porphyrin was isolated from the reaction mixture. To understand why only two of the four enthynyl groups undergo Bergman cyclization, the reaction coordinates were examined by using DFT at the PWPW91/cc‐pVTZ(‐f) level coupled to a continuum solvation model. The barrier to cyclization of the second pair of ethynyl groups was found to be 5.5 kcal mol^?1 higher than the first, suggesting a negative cooperative effect and significantly slower rate for the second cyclization. Cyclization reactions for model porphyrin–enediynes with ethene‐ and H‐functionality substitutions at the meso‐phenyl rings were also examined, and found to have a similar barrier to diradical formation for the second cyclization event as for the first in these highly planar molecules. By enforcing an artificial 30° cant in two of the pyrrole rings of the porphyrin, the second barrier was increased by 2 kcal mol^?1 in the ethene model system; this suggests that the disruption of the π conjugation of the extended porphyrin structure is the cause of the increased barrier to the second cyclization event.     

Chemical synthesis, crystal structure and enzymatic evaluation of a dinucleotide spore photoproduct analogue containing a formacetal linker

Spore photoproduct (SP) is the exclusive DNA photodamage product found in bacterial endospores. Its photoformation and repair by a metalloenzyme spore photoproduct lyase (SPL) composes the unique SP biochemistry. Despite the fact that the SP was discovered almost 50 years ago, its crystal structure is still unknown and the lack of structural information greatly hinders the study of SP biochemistry. Employing a formacetal linker and organic synthesis, we successfully prepared a dinucleotide SP isostere 5R-CH(2) SP, which contains a neutral CH(2) moiety between the two thymine residues instead of a phosphate. The neutral linker dramatically facilitates the crystallization process, allowing us to obtain the crystal structure for this intriguing thymine dimer half a century after its discovery. Further ROESY spectroscopic, DFT computational, and enzymatic studies of this 5R-CH(2) SP compound prove that it possesses similar properties with the 5R-SP species, suggesting that the revealed structure truly reflects that of SP generated in Nature.