Pheophytin a and chlorophyll a have been investigated by electrospray mass spectrometry in the positive and negative modes, in view of the importance of the knowledge of their properties in photosynthesis. Pheophytin and chlorophyll are both observed intensely in the protonated mode, and their main fragmentation route is the loss of their phytyl chain. Pheophytin is observed intact in the negative mode, while under collisions, it is primarily cleaved beyond the phytyl chain and loses the attaching propionate group.
View Article and Find Full Text PDFPeptides and foldamers have recently gained increasing attention as chiral catalysts to achieve challenging (asymmetric) transformations. We previously reported that short helically folded aliphatic oligoureas in combination with achiral Brønsted bases are effective H-bonding catalysts for C-C bond-forming reactions─i.e.
View Article and Find Full Text PDFA valence coordinate HNOH ground state potential energy surface accurate for all levels up to 6000 cm relative to trans zero point energy has been generated at the coupled-cluster single double triple-F12/aug-cc-pVTZ level encompassing the trans and cis as well as the N-H permutational conformers. All cis and trans fundamentals and a complete set of eigenfunctions up to about 3100 cm have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The average and maximal error to all observed transitions is about 6.
View Article and Find Full Text PDFCRYSTAL is a periodic ab initio code that uses a Gaussian-type basis set to express crystalline orbitals (i.e., Bloch functions).
View Article and Find Full Text PDFAn extension of the CRYSTAL program is presented allowing for calculations of anharmonic infrared (IR) intensities and Raman activities for periodic systems. This work is a follow-up of two papers devoted to the computation of anharmonic vibrational states of solids from DFT (density functional theory) calculations (Erba et al. 2019, 15, 3755-3765 and Erba et al.
View Article and Find Full Text PDF