Suppressing one‐bond homonuclear 13C,13C scalar couplings in the J‐HMBC NMR experiment: application to 13C site‐specifically labeled oligosaccharides

Site‐specific ¹³C isotope labeling is a useful approach that allows for the measurement of homonuclear ¹³C,¹³C coupling constants. For three site‐specifically labeled oligosaccharides, it is demonstrated that using the J‐HMBC experiment for measuring heteronuclear long‐range coupling constants is problematical for the carbons adjacent to the spin label. By incorporating either a selective inversion pulse or a constant‐time element in the pulse sequence, the interference from one‐bond ¹³C,¹³C scalar couplings is suppressed, allowing the coupling constants of interest to be measured without complications. Experimental spectra are compared with spectra of a nonlabeled compound as well as with simulated spectra. The work extends the use of the J‐HMBC experiments to site‐specifically labeled molecules, thereby increasing the number of coupling constants that can be obtained from a single preparation of a molecule. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectral line narrowing of a photonically generated microwave frequency comb with vertical-cavity surface-emitting laser mode-locked coupled oscillators

A technique is presented for narrowing the spectral linewidth of microwave signals generated photonically by heterodyning a pair of vertical-cavity surface-emitting lasers forming an extended optically coupled cavity. The experimentally demonstrated linewidth reduction, by as much as a factor of 10(4)--to less than 10 kHz in microwave frequencies up to a couple of gigahertz--is approximately ten times that expected with conventional line-narrowing techniques such as optical feedback. An interpretation is given in terms of mode locking in pairs of optically coupled lasers as a first demonstration in the frequency domain of lag synchronization of coupled oscillators. The results of theoretical modeling agree well with the experimental results.     

Erratum to: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

This is a correction to the following paper: Hague T, Petroczi A, Andrews PR, Barker J, Naughton DP: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Central J 2008, 2:13.     

Estimation of the specific mass effect in the isotope shifts of energy levels in the optical spectrum of Ba I and Ba II

A graphical method for separating mass and volume effects from purely optical isotope shift data is presented and compared with King's “bunching” method. Recent experimental data on isotope shifts for a wide range of spectral lines in the naturally abundant isotopes of Ba I and Ba II are analysed. Some agreement is found with muonicx-ray data concerning the nuclear size for the isotopes 136, 137 and 138, but there is disagreement (over 20%) for the other isotopes. Thelevel isotope shifts are further parameterised in terms of a linear model, and the specific mass effect is decomposed into sums of one-electron and two-electron shift parameters with respect to the inert-gas like ground state of Ba III.     

Thallium hyperfine anomaly

Measurements of the hyperfine structure in the highly charged hydrogen like systems ²⁰³Tl⁸⁰⁺ and ²⁰⁵Tl⁸⁰⁺ are underway at the Super EBIT at LLNL. This work considers the effects of the nuclear magnetization distribution on the hyperfine structure. The difference in energy splitting due to hyperfine structure for ²⁰³Tl and ²⁰⁵Tl, respectively, is found to be 0.031 04(1) eV, which corresponds to a transition wavelength difference of 3.640(1) nm. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

Background  

Considerable research has been directed towards the roles of metal ions in nutrition with metal ion toxicity attracting particular attention. The aim of this study is to measure the levels of metal ions found in selected beverages (red wine, stout and apple juice) and to determine their potential detrimental effects via calculation of the Target Hazard Quotients (THQ) for 250 mL daily consumption.     

NMR analysis of conformationally dependent (n)J(C, H) and (n)J(C, C) in the trisaccharide α-L-Rhap-(1 → 2)[α-L-Rhap-(1 → 3)]-α-L-Rhap-OMe and a site-specifically labeled isotopologue thereof

An array of NMR spectroscopy experiments have been carried out to obtain conformationally dependent (1)H,(13)C- and (13)C,(13)C-spin-spin coupling constants in the trisaccharide α-L-Rhap-(1 → 2)[α-L-Rhap-(1 → 3)]-α-L-Rhap-OMe. The trisaccharide was synthesized with (13)C site-specific labeling at C2' and C2″, i.e. in the rhamnosyl groups in order to alleviate (1)H spectral overlap. This facilitated the measurement of a key trans-glycosidic proton-proton cross-relaxation rate using 1D (1)H,(1)H-T-ROESY experiments as well as a (3)J(C, H) coupling employing 1D (1)H,(13)C-long-range experiments, devoid of potential interference from additional J coupling. By means of both the natural abundance compound and the (13)C-labeled sample 2D (1)H,(13)C-J-HMBC and (1)H,(13)C-HSQC-HECADE NMR experiments, total line-shape analysis of (1)H NMR spectra and 1D (13)C NMR experiments were employed to extract (3)J(C, H) , (2)J(C, H), (3)J(C, C), and (1)J(C, C) coupling constants. The (13)C site-specific labeling facilitates straightforward determination of (n)J(C, C) as the splitting of the (13)C natural abundance resonances. This study resulted in eight conformationally dependent coupling constants for the trisaccharide and illustrates the use of (13)C site-specific labeling as a valuable approach that extends the 1D and 2D NMR methods in current use to attain both hetero- and homonuclear spin-spin coupling constants that subsequently can be utilized for conformational analysis.