Prüfung der Butter auf Verfälschung mit anderen Fetten

Analytical and Bioanalytical Chemistry -     

High rate performance of lithium manganese nitride and oxynitride as negative electrodes in lithium batteries

The performance of Li_7.9MnN_3.2O_1.6 and Li₇MnN₄ as electrode materials in lithium batteries was analyzed. At 1C rate, capacities of 180 and 230 mAh/g, respectively, were obtained after 50 cycles. If the first charge is done at 0.1C, outstanding capacities of 120–135 mAh/g are observed after 100 cycles at 5C. More lithium can be removed during the charge at 0.1C, leading to a large amount of lithium vacancies that enhance mobility and rate capability. It is proposed that incomplete filling of the vacancies occurs upon cycling, so that the mobility remains high. This performance compares well to that of Li₄Ti₅O₁₂.     

An analytical strategy for quaternary ammonium neuromuscular blocking agents in a forensic setting using LC-MS/MS on a tandem quadrupole/time-of-flight instrument

An analytical strategy is described for analyzing quaternary ammonium neuromuscular blocking agents in a wide variety of biological specimens in a forensic setting. Neuromuscular blocking agents such as succinylcholine, pancuronium, and tubocurarine, often used as paralytic agents during surgery, are occasionally suspected as paralytic poisoning agents involved in suspected homicide and suicide cases. Because suspicion in such cases can develop slowly, the age, nature, and quality of available specimens varies greatly. The compounds are challenging analytically because of their simultaneous precharged yet lipophilic character. An analytical strategy has been devised for extracting these compounds from complex matrices using a combination of a modified Bligh and Dyer liquid-liquid extraction (used in reverse) followed by reverse-phase ion pairing solid-phase extraction using heptafluorobutyric acid as an ion pairing reagent. Final analysis is by LC-MS/MS using a tandem quadrupole orthogonal acceleration time of flight instrument (Q-TOF) with repetitive product ion scanning at high resolution. Native and spiked specimens are compared for both quantitative and especially qualitative purposes. The method has been applied to a wide variety of fluid and tissue specimen types, including numerous specimens from exhumation autopsies. For most specimens, detection limits are in the 2 to 10 ng/g range. Succinylmonocholine has been demonstrated to be present at low levels in normal posthumous kidney and liver. The Q-TOF is an excellent platform for forensic analytical investigations. This analytical strategy should also be applicable to other problematic analytes and sample matrices.     

Charge accumulation and polarization in titanium dioxide electrodes

Nanocrystalline TiO(2) electrodes were studied spectroelectrochemically by observing the simultaneous relaxation of the current and absorbance after applying a voltage step. The absorbance behaved differently in two time regimes: (1) ionic polarization in the oxide electrode, in which charged ions, such as Ti(3+) sites and/or interstitial Ti(4+) sites, move in response to the applied electric field, and (2) the diffusion of Li(+) ions into the TiO(2). These two behaviors were analyzed with equivalent circuit models. Li(+) ions reduce the resistance of the TiO(2) by approximately 90%, increase the capacitance by approximately 350%, and decrease the inductance by approximately 30%. Voltage cycling produces a buildup of intercalated Li(+) ions, lessening the electrode's response to the potential step, and causing it to become a more efficient inductor. The potential distribution in the nanoparticles is described by using a dielectric model in which roughly half the applied potential is dropped across the interface with a Li(+)-ion-containing electrolyte.     

On a singular minimizing problem

We investigate the non-homogeneous modular Dirichlet problem Δ _p (·)u(x) = f (x) (where Δ _p (·)u(x) = div(|?u|^p(x-2)?u(x)) from the functional analytic point of view and we prove the stability of the solutions \({\left( {{u_{{p_i}}}} \right)_i}\) of the equation \({\Delta _{{p_i}\left( \cdot \right)}}{u_{{p_i}\left( \cdot \right)}} = f\) as p _i (·) → q(·) via Gamma-convergence of sequence of appropriate functionals.     

Die Pasteursche Methode zur Bestimmung der Bernsteins?ure neben anderen bei der G?rung entstehenden S?uren hat

Ohne Zusammenfassung     

Kohlenhydrate

Ohne Zusammenfassung     

Disulfide bond isomerization in basic pancreatic trypsin inhibitor: multisite chemical exchange quantified by CPMG relaxation dispersion and chemical shift modeling

Conformational changes occurring on the microsecond-millisecond time scale in basic pancreatic trypsin inhibitor (BPTI) are investigated using nuclear magnetic resonance spectroscopy. The rczz CPMG experiment (Wang, C.; Grey, M. J.; Palmer, A. G. J. Biomol. NMR 2001, 21, 361-366) is used to record (15)N spin relaxation dispersion data, R(ex)(1/tau(cp)), in which 1/tau(cp) is the pulsing rate in the CPMG sequence, at two static magnetic fields, 11.7 and 14.1 T, and three temperatures, 280, 290, and 300 K. These data are used to characterize the kinetics and mechanism of chemical exchange line broadening of the backbone (15)N spins of Cys 14, Lys 15, Cys 38, and Arg 39 in BPTI. Line broadening is found to result from two processes: the previously identified isomerization of the Cys 38 side chain between chi(1) rotamers (Otting, G.; Liepinsh, E.; Wüthrich, K. Biochemistry 1993, 32, 3571-3582) and a previously uncharacterized process on a faster time scale. At 300 K, both processes contribute significantly to the relaxation dispersion for Cys 14 and an analytical expression for a linear three-site exchange model is used to analyze the data. At 280 K, isomerization of the Cys 38 side chain is negligibly slow and the faster process dominates the relaxation dispersion for all four spins. Global analysis of the temperature and static field dependence of R(ex)(1/tau(cp)) for Cys 14 and Lys 15 is used to determine the activation parameters and chemical shift changes for the previously uncharacterized chemical exchange process. Through an analysis of a database of chemical shifts, (15)N chemical shift changes for Cys 14 and Lys 15 are interpreted to result from a chi(1) rotamer transition of Cys 14 that converts the Cys 14-Cys 38 disulfide bond between right- and left-handed conformations. At 290 K, isomerization of Cys 14 occurs with a forward and reverse rate constant of 35 s(-1) and 2500 s(-1), respectively, a time scale more than 30-fold faster than the Cys 38 chi(1) isomerization. A comparison of the kinetics and thermodynamics for the transitions between the two alternative Cys 14-Cys 38 conformations highlights the factors that affect the contribution of disulfide bonds to protein stability.     

Origin of the tailing signal on the low-energy side of the main beam in mass-analyzed ion kinetic energy spectra

The tailing signal on the low-energy side of the precursor ion signal observed during fast atom bombardment (FAB) mass-analyzed ion kinetic energy spectrometric (MIKES) analyses is due largely to ions of higher m/z value than the chosen precursor. The majority of these ions are independent, unfragmented species that emerge from the ion source with less than the full amount of kinetic energy predicted by the source potential. The tailing precursor ion signal observed under helium collision-activated decomposition conditions is too short to account for the protracted MIKES tail (as judged from mass-to-charge ratio-deconvoluted MIKES analyses performed on a BEqQ hybrid instrument), and a tailing precursor signal is not observed under unimolecular decomposition conditions. Measurements of the mass-to-charge ratios of the ionic species comprising the MIKES tail demonstrated that ions higher in mass-to-charge ratio than the chosen precursor are present throughout the tail, with the mass-to-charge ratio increasing as kinetic energy decreases. These ions possess the same momentum as the chosen precursor, and thus were formed prior to the magnetic field. The existence of intact, source-formed [M + H]⁺ ions with reduced kinetic energy was demonstrated through several types of tandem mass spectrometric experiments. These [M + H]⁺ ions with reduced kinetic energy do not appear to have undergone collisional deceleration, because they do not possess increased internal energy (as judged by observation of their fragmentation patterns). The kinetic energy profiles of unfragmented FAB-desorbed ions were determined and found to exhibit a tailing character similar in appearance to that of the MIKES tail. The population of ions emerging from the source under FAB conditions thus incorporates the characteristics necessary to account for the MIKES tail, namely, the presence of ions of a mass-to-charge ratio higher than the chosen precursor (due to matrix and other background ions), which possess reduced kinetic energy such that their momentum is identical to that of the selected precursor. These ions may arise via desolvation and declustering processes in the acceleration region of the ion source, or via FAB or chemical ionization processes in regions removed from the FAB target.