The 1H and 13C NMR chemical shifts of Strychnos alkaloids revisited at the DFT level

The density functional theory calculation of ¹H and ¹³C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated ¹H and ¹³C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases.     

EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Temporary attachment of carbohydrates to cyclopeptide templates: a new strategy for single-bead analysis of multivalent neoglycopeptides

Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time.     

Dynamic interaction of plasma flow with the hot boundary layer of a geomagnetic trap

The study of the interaction between collisionless plasma flow and stagnant plasma revealed the presence of an outer boundary layer at the border of a geomagnetic trap, where the super-Alfvén subsonic laminar flow changes over to the dynamic regime characterized by the formation of accelerated magnetosonic jets and decelerated Alfvén flows with characteristic relaxation times of 10–20 min. The nonlinear interaction of fluctuations in the initial flow with the waves reflected from an obstacle explains the observed flow chaotization. The Cherenkov resonance of the magnetosonic jet with the fluctuation beats between the boundary layer and the incoming flow is the possible mechanism of its formation. In the flow reference system, the incoming particles are accelerated by the electric fields at the border of boundary layer that arise self-consistently as a result of the preceding wave-particle interactions; the inertial drift of the incoming ions in a transverse electric field increasing toward the border explains quantitatively the observed ion acceleration. The magnetosonic jets may carry away downstream up to a half of the unperturbed flow momentum, and their dynamic pressure is an order of magnitude higher than the magnetic pressure at the obstacle border. The appearance of nonequilibrium jets and the boundary-layer fluctuations are synchronized by the magnetosonic oscillations of the incoming flow at frequencies of 1–2 mHz.     

Exceptional Θ-Correspondences I

Let G be either a split SO(2n+2), or a split adjoint group of type En, (n=6,7,8), over a p-adic field. In this article we study correspondences arising by restricting the minimal representation of G to various dual pairs in G.     

Algorithmic and explicit determination of the Lovász number for certain circulant graphs

We consider the problem of computing the Lovász theta function for circulant graphs C_n,J of degree four with n vertices and chord length J, 2?J?n. We present an algorithm that takes O(J) operations if J is an odd number, and O(n/J) operations if J is even. On the considered class of graphs our algorithm strongly outperforms the known algorithms for theta function computation. We also provide explicit formulas for the important special cases J=2 and J=3.     

Phase transition in iodine: a chemical picture

The phase transition under pressure in iodine is analyzed using the electron localization function (ELF), explaining that the increase of the c/a ratio under compression is due to the presence of the lone pairs.A probabilistic interpretation is given for ELF.