Exploring new 129Xe chemical shift ranges in HXeY compounds: hydrogen more relativistic than xenon

Among rare gases, xenon features an unusually broad nuclear magnetic resonance (NMR) chemical shift range in its compounds and as a non-bonded Xe atom introduced into different environments. In this work we show that (129)Xe NMR chemical shifts in the recently prepared, matrix-isolated xenon compounds appear in new, so far unexplored (129)Xe chemical shift ranges. State-of-the-art theoretical predictions of NMR chemical shifts in compounds of general formula HXeY (Y = H, F, Cl, Br, I, -CN, -NC, -CCH, -CCCCH, -CCCN, -CCXeH, -OXeH, -OH, -SH) as well as in the recently prepared ClXeCN and ClXeNC species are reported. The bonding situation of Xe in the studied compounds is rather different from the previously characterized cases as Xe appears in the electronic state corresponding to a situation with a low formal oxidation state, between I and II in these compounds. Accordingly, the predicted (129)Xe chemical shifts occur in new NMR ranges for this nucleus: ca. 500-1000 ppm (wrt Xe gas) for HXeY species and ca. 1100-1600 ppm for ClXeCN and ClXeNC. These new ranges fall between those corresponding to the weakly-bonded Xe(0) atom in guest-host systems (δ < 300 ppm) and in the hitherto characterized Xe molecules (δ > 2000 ppm). The importance of relativistic effects is discussed. Relativistic effects only slightly modulate the (129)Xe chemical shift that is obtained already at the nonrelativistic CCSD(T) level. In contrast, spin-orbit-induced shielding effects on the (1)H chemical shifts of the H1 atom directly bonded to the Xe center largely overwhelm the nonrelativistic deshielding effects. This leads to an overall negative (1)H chemical shift in the range between -5 and -25 ppm (wrt CH(4)). Thus, the relativistic effects induced by the heavy Xe atom appear considerably more important for the chemical shift of the neighbouring, light hydrogen atom than that of the Xe nucleus itself. The predicted NMR parameters facilitate an unambiguous experimental identification of these novel compounds.     

Two-Photon Excited Fluorescence Energy Transfer: A Study Based on Oligonucleotide Rulers

The use of two-photon excitation of fluorescence for detection of fluorescence resonance energy transfer (FRET) was studied for a selected fluorescent donor–acceptor pair. A method based on labeled DNA was developed for controlling the distance between the donor and the acceptor molecules. The method consists of hybridization of fluorescent oligonucleotides to a complementary single-stranded target DNA. As the efficiency of FRET is strongly distance dependent, energy transfer does not occur unless the fluorescent oligonucleotides and the target DNA are hybridized. A high degree of DNA hybridization and an excellent FRET efficiency were verified with one-photon excited fluorescence studies. Excitation spectra of fluorophores are usually wider in case of two-photon excitation than in the case of one-photon excitation [1]. This makes the selective excitation of donor difficult and might cause errors in detection of FRET with two-photon excited fluorescence. Different techniques to analyze the FRET efficiency from two-photon excited fluorescence data are discussed. The quenching of the donor fluorescence intensity turned to be the most consistent way to detect the FRET efficiency. The two-photon excited FRET is shown to give a good response to the distance between the donor and the acceptor molecules.     

Polar sets on metric spaces

We show that if is a proper metric measure space equipped with a doubling measure supporting a Poincaré inequality, then subsets of with zero -capacity are precisely the -polar sets; that is, a relatively compact subset of a domain in is of zero -capacity if and only if there exists a -superharmonic function whose set of singularities contains the given set. In addition, we prove that if is a -hyperbolic metric space, then the -superharmonic function can be required to be -superharmonic on the entire space . We also study the the following question: If a set is of zero -capacity, does there exist a -superharmonic function whose set of singularities is precisely the given set?

     

Density functional calculations of 3He chemical shift in endohedral helium fullerenes: Neutral, anionic, and di-helium species

We report density functional calculations of 3He nuclear magnetic resonance chemical shifts in a series of experimentally known endohedral helium fullerenes, He(n)@Cm(q) (n = 1, 2; m = 60, 70, 76, 78; q = 0, 6-), including for the first time anionic and di-helium species. Despite the lack of dispersion in the density functional model, the results are in promising agreement with experiment. Density functional theory performs better than Hartree-Fock for the anionic systems. In the di-helium species confined in the small C60 cage, besides the atomic displacements from the center position, the direct He-He interactions contribute to the 3He shift.     

Direct determination of absolute configuration of carboxylic acids by cyclooctapyrrole

Octaphyrin O1 has been found to be an effective sensor for the direct determination of absolute configuration of a variety of carboxylic acids at mM concentrations at room temperature based on CD exciton chirality method.