Simultaneous quantification of terpenelactones and flavonol aglycones in hydrolyzed ginkgo biloba extract by liquid chromatography with inline ultraviolet and evaporative light scattering detection

We report here a liquid chromatography (LC) method with inline ultraviolet/evaporative light scattering (UV/ELS) detection for the simultaneous quantification of the terpenelactones and flavonol aglycones in a single sample of hydrolyzed Ginkgo biloba extract (GBE). The sample is hydrolyzed by a rapid and convenient oven heating method for 1 h at 90 degrees C with 10% hydrochloric acid. The 1 h hydrolysis was found to be equivalent to the 2.25 h reflux treatment for dry powder extract, where total flavonol glycosides were 28.4 and 28.1%, respectively. Acceptable precision was achieved for total terpenelactones [relative standard deviation (RSD) = 4.8%] by ELS detection, and total flavonol aglycones (RSD = 2.3%) by UV detection. The analytical range was 1.5 to 7.3% (w/w) for the individual terpenelactones (ELS) and 2.5 to 15.0% (w/w) for the individual glycosides (UV) calculated from the aglycones quercetin, kaempferol, and isorhamnetin. This improved method allows for the first time high throughput sample preparation coupled with the quantification of the predominant compounds generally used for quality control of GBE in a single assay.     

The influence of aliphatic diols on the temperature of maximum density of water

The influence of various aliphatic diols on the temperature of maximum density (TMD) of water has been investigated. 1,2-Propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2,5-hexanediol were found to yield positive structural contributions to the solute-induced shift in the TMD, i.e., they are structure makers. Contrariwise, data from the literature indicate that 1,2-ethanediol is a structure breaker. Relationships between the structure making/breaking tendencies of the solutes and the relative positions of the two hydroxyl groups are discussed.     

Dynamical phases of the Hindmarsh-Rose neuronal model: studies of the transition from bursting to spiking chaos

The dynamical phases of the Hindmarsh-Rose neuronal model are analyzed in detail by varying the external current I. For increasing current values, the model exhibits a peculiar cascade of nonchaotic and chaotic period-adding bifurcations leading the system from the silent regime to a chaotic state dominated by bursting events. At higher I-values, this phase is substituted by a regime of continuous chaotic spiking and finally via an inverse period doubling cascade the system returns to silence. The analysis is focused on the transition between the two chaotic phases displayed by the model: one dominated by spiking dynamics and the other by bursts. At the transition an abrupt shrinking of the attractor size associated with a sharp peak in the maximal Lyapunov exponent is observable. However, the transition appears to be continuous and smoothed out over a finite current interval, where bursts and spikes coexist. The beginning of the transition (from the bursting side) is signaled from a structural modification in the interspike interval return map. This change in the map shape is associated with the disappearance of the family of solutions responsible for the onset of the bursting chaos. The successive passage from bursting to spiking chaos is associated with a progressive pruning of unstable long-lasting bursts.     

On functions having Cauchy differences in some prescribed sets

Summary AssumeE is a real topological vector space,F is a real Banach space,K is a discrete subgroup ofF andC is a symmetric, convex and compact subset ofF such thatK (6C) = {0}. If a functionh:E F is continuous at at least one point andh(x + y) – h(x) – h(y) K + C for allx, y E, then there exists a continuous linear functiona:E F such thath(x) – a(x) K + C for everyx E.     

Conformers of gaseous protonated glycine

Ab initio geometry optimizations were performed on gaseous protonated glycine using the second-order Møller–Plesset perturbation theory with the 6-31G*, 6-31G**, 6-31+G**, and 6-311+G** basis sets. Eight energy minima and 12 saddle points in the low-energy region of the electronic potential energy surface were characterized. The global minimum was an amino N-protonated conformer containing an ionic H bond between the (SINGLE BOND)NH₃⁺ and O(DOUBLE BOND)C(DIAGONAL BOND)(DIAGONAL BOND) groups. The lowest energy O-protonated conformer was stabilized by a conjugative attraction between the nitrogen lone-pair electrons and the positively charged planar fragment (SINGLE BOND)C(OH)₂⁺. Relative electronic energies of the nine N- and 11 O-protonated species fall in the ranges of 0–10 and 30–40 kcal mol⁻¹. At room temperature the equilibrium distribution contained the most stable N-protonated conformer almost exclusively. Additional subjects for investigation include the effects of basis set and electron correlation on the predicted structures, nonbonded interactions that influence the relative stability of protonated conformers, conformational interconversions based on intrinsic reaction coordinate calculations, and kinetic pathways for protonation and associated changes in Gibbs free energy. The work provides geometric, energetic, and thermodynamic data pertinent to the study of gas-phase ion chemistry of amino acids and peptides. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1862–1876, 1998     

Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica Architectures

New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p‐divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 10⁸ Hz at 325 K), as detected by solid‐state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I₂ vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl‐fluoro‐phenylene rotors, affecting their motion and the dielectric properties.