Enhanced comprehensive two-dimensional gas chromatographic resolution of polychlorinated biphenyls on a non-polar polysiloxane and an ionic liquid column series

A total of 196 out of 209 polychlorobiphenyl (PCB) congeners were resolved using GC×GC-TOFMS with a non-polar/ionic liquid column series consisting of poly(50%-n-octyl-50%-methyl)siloxane and (1,12-di(tripropylphosphonium)dodecane bis(trifluoromethansulfonyl)amide) in the first and second dimension, respectively. It has been found that 13 PCB congeners overlap in five doublets (CB12+CB13, CB62+CB75, CB70+CB76, CB97+CB125 and CB153+CB168) and one triplet (CB90+CB101+CB113). All toxic, "dioxin like" congeners were separated with no interferences from any PCB congener. The 109 PCBs present in Aroclor 1242 and the 82 PCBs present in Aroclor 1260 were resolved GC×GC-TOFMS analysis on this column set.     

On the origins of core-electron chemical shifts of small biomolecules in aqueous solution: insights from photoemission and ab initio calculations of glycine(aq)

The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon 1s binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.     

Visualization of Protein‐Specific Glycosylation inside Living Cells

Protein glycosylation is a ubiquitous post‐translational modification that is involved in the regulation of many aspects of protein function. In order to uncover the biological roles of this modification, imaging the glycosylation state of specific proteins within living cells would be of fundamental importance. To date, however, this has not been achieved. Herein, we demonstrate protein‐specific detection of the glycosylation of the intracellular proteins OGT, Foxo1, p53, and Akt1 in living cells. Our generally applicable approach relies on Diels–Alder chemistry to fluorescently label intracellular carbohydrates through metabolic engineering. The target proteins are tagged with enhanced green fluorescent protein (EGFP). Förster resonance energy transfer (FRET) between the EGFP and the glycan‐anchored fluorophore is detected with high contrast even in presence of a large excess of acceptor fluorophores by fluorescence lifetime imaging microscopy (FLIM).     

Detection of aniline at boron-doped diamond electrodes with cathodic stripping voltammetry

Boron-doped diamond (BDD) electrodes were used to investigate the possibility of detecting aniline by linear-sweep cathodic stripping voltammetry. It was found that the dimeric species (p-aminodiphenylamine and benzidine) formed by anodic oxidation of aniline during the accumulation period are involved in electrochemically reversible redox processes and, in acidic media, the shape of the stripping voltammetric response is suitable for aniline detection in the micromolar concentration range. The low background current of conductive diamond is an advantage compared to other electrode materials and allows a detection limit of 1 μM. Weak adsorption properties and the extreme electrochemical stability are additional advantages of BDD and it was found that, even after long-time measurements, the electrode surface can regain its initial activity by an anodic polarization in the potential region of water decomposition.     

Distorted five-fold coordination of Cu2+(aq) from a Car-Parrinello molecular dynamics simulation

The solvation shell structure and dynamics of a single Cu2+ ion in a periodic box with 32 water molecules under ambient conditions has been investigated using Car-Parrinello molecular dynamics simulations in a time-window of 18 ps. Five-fold coordination with four equidistant equatorial water molecules at 2.00 A and one axial water molecule at 2.45 A from the Cu2+ ion is found. A "hole" without water molecules is found on the opposite side of the axial water. The ion-water bonding character for the equatorial water molecules is different from that of the axial water molecules, as shown by a localized orbital analysis of the electronic structure. Moreover, the calculated OD stretching vibrational band for the equatorial water molecules lies ca. 175 cm-1 below the axial-water band, in good agreement with experimental data. The equatorial-water band lies below, and the axial-water band above, the pure liquid D2O band, also in agreement with experimental data.     

Azin­yl sulfides. LXXXI. 14‐Phen­yl‐7‐thia­pyrano[2,3‐c;6,5‐c′]diquinoline‐14‐carbonitrile

The mol­ecules of the title compound, C₂₆H₁₅N₃S, have a penta­cyclic ring system which is almost planar, with the central ring in a flattened boat conformation. The folding angle between the two quinoline rings is 6.75 (7)°. The 14‐phen­yl substituent is in a quasi‐axial conformation, while the 14‐cyano substituent is in a quasi‐equatorial conformation with respect to the thio­pyran ring. The S⋯C—C_phen­yl and S⋯C—C_CN angles are 116.8 (2) and 129.3 (2)°, respectively. The plane of the phen­yl group is nearly coplanar with the plane bis­ecting the dihedral angle of the penta­cyclic ring system.     

Computerized separation of chromatographically unresolved peaks

A computerized peak deconvolution software and mass spectra were successfully applied for the deconvolution of overlapped peak cluster in the chromatogram obtained separating the complex mixture of pesticides by retention time locking gas chromatography-mass spectroscopy. The method based on the unique fragment ions in the spectra can be used for deconvolution of peak clusters if mass spectra of overlapped peaks differ. This method allows determining actual retention times of overlapped peaks. Peak areas found by this method however, cannot be used naturally for the quantitative purposes as the abundance of fragment ions used for this deconvolution procedure can dramatically differ. Computer assisted deconvolution of peaks in the peak clusters gives more realistic peak area ratios as at this method it is supposed equal response for all peaks overlapped in a cluster.     

Hydrophilic Carotenoids: Surface Properties and Aggregation Behavior of the Potassium Salt of the Highly Unsaturated Diacid Norbixin

The oft‐claimed ‘good’ water solubility of the food color norbixin ( 3 ) could not be confirmed. In contrast, the potassium salt 5 of norbixin formed suitable dispersions. The surface and aggregation properties of salt 5 were investigated and compared with other naturally occurring and synthetic hydrophilic carotenoids (Table).     

Domains of holomorphy for Fourier transforms of solutions to discrete convolution equations

We study solutions to convolution equations for functions with discrete support in R~n, a special case being functions with support in the integer points. The Fourier transform of a solution can be extended to a holomorphic function in some domains in C~n, and we determine possible domains in terms of the properties of the convolution operator.